~~

Equilibrium II:
Acids and Bases

1 1~l j~r[I\l I1 Irilllilfil~l l

N27900
 · "'-.{/

~:&G1 b,~

~ Inner London Educa t i on Authority 1983

First publis hed 198 3

by John Murray (Publishers) Lt d
50 Al be mar l e St r e e t
London W1X 4BD

Repri nt ed 1984 , 198 5, 1987

All rights rese rved.

Unaut horised duplic ation
contr avenes applicabl e l aws

Pri nted in Great Britain by

Ma r ti n ' s of Berwick

British Library Catalo guing in Publ ication Dat a

Independ en t Learning Project for Advanced
Che mi s t r y
Equili brium II : Acid s and Bases . - (ILPAC; Unit P3)
1 . Sc i e nce
I . Ti t l e I I . Se r ie s
500 Q16 1 .2

ISBN 0 7195 4041 0

ii
CONTENTS
~

PREFACE v
Acknowl edgeme nt s vi
Key to a ct i vit y sy mbol s a nd ha zard s ymbol s vii

INTRODUCT ION 1
Pr e- knowl e dge 1
Pre-test 3

LEVE L ONE 5
HYDROGEN I ONS 5
Si ze of hydroge n i ons 5
Hyd r ogen ions in solution 5
Fur t he r hydration of H3 0 + 6
At trac t io n of hydrog e n ion s by o t her c e nt res of nega t ive cha rg e 7
THE BR0NSTED- LOWRY THEORY 8
Co nj uga t e ac id -ba se pa irs 8
Amphi pro t i c sub sta nce s 11
IONIZATION OF WATER 12
The ionic pr od uc t of water 12
Using the expres s io n f or the ionic product of wate r 14
The e f f ec t of tempe rat ur e on Kw 15
pH , THE HYDRO GE N I ON EXPO NENT 16
The pH s cale 18
Ca lc ulat ing pH f rom hyd roge n ion conc ent ra t i on 20
Calcu l a ting hyd rogen i o n concent ration from pH 21
RE LATIVE STRENGTHS OF ACIDS 23
Experimen t 1 - t he pH of a weak a cid at vari ou s conc ent rat io ns 24
Experiment 2 - t he pH of diffe re nt a ci ds at t he same c on c en trati on 26
Disso c i ation cons ta nts of ac i ds 27
Calcu l a ting Ka f rom hydro ge n i on conc ent r a t io n (o r f rom pH) 28
Calc ula t ing pH f rom t he disso ciation const a nt 30
BUFFER SO LUTIONS (1) : CONTROLLING THE pH 32
Experi me nt 3 - t he a c ti on of a buff er so lu t io n 32
Com pos ition of bu ffer solutions 35
How a cid buffe rs abso rb hyd rogen ions a nd hydro xi de i ons 35
Buffe r sol ut ions a nd t he equ ilib ri um law 37
HISTORICAL DEVELO PME NT OF ACID-BASE THEORIE S 40
LEVEL ONE CHECK LIS T 41
LEVEL ONE TEST 43

LEVEL TWO
ACID -BASE INDICATORS 45
Expe r i ment 4 - det e rmini ng t he pH ran ge of s ome a ci d-ba s e indica tors 45
Ind icato rs as weak aci ds 48
End-point a nd equi valence point 49
Choice of i ndi c ato r 49
Calcu l at i ng t he pH r an ge of an i ndi ca t or 51
Meas urement of KI n va l ues f or indica t or s 52
Expe r i ment 5 - det e rmining the io ni zat i on c ons t ant for a n i ndi ca tor 52
pH CHANGES DURING TI TRATI ONS 56
Expe r i ment 6 - obt a ining pH curves f or a c i d- a l ka li t itra t ion s 57
pH c urves by ca lcu lat io n 61
pH cu rves by c omput e r 62
HYDROLY SIS OF SALTS 63

iji
BUffER SOLUTIONS (2) 64
Buff ering r egions of titrati on curves 64
pH of a buffer soluti on 66
Contamination of buffer solution s 66
Basic buff ers 69
The relation sh ip betwe en pH , Ka and composition of a buff er 70
Ca lc ul at i ng t he c ompos i t io n of a buffe r from pH 71
Choosing subst ances for a buff er so lu tio n 73
Experime nt 7 - prep aration of buffers : t e sting their buf fe r i ng
capac it y and the e f fe ct of dil utio n 74
Buffers a nd di l ut i on 75
Experiment 8 - determ inin g the dissociation con sta nt for a wea k
acid using a n i ndi ca t or 77
LEVEL TWO CHECKLI ST 79

END-Of -UNIT TEST 81

APP ENDI X ON E
Ad di tiona l exerci ses 85

APP ENDIX TWO

Calculatin g the pH of sa l t solutio ns 89

AN SWER S TO EXERCI SES 91

iv
PREFACE

This vo l ume i s on e of twenty Un i t s pr oduced by IL PAC, the I nde pe nd e nt Learning

Projec t f or Adva nced Che mis t ry , written f o r s t udents pre pa r i ng for the Advanced
Le vel examina t i o ns of the G.C.E. The Pr o jec t has be en s po nso re d by the Inner
Lond on Education Authorit y and th e material s hav e bee n e xt e ns i ve l y tested in
London schoo ls an d coll e ge s . I n it s pres en t r e vi s e d fo rm , howeve r , i t is
i nt end ed f or a wi der audience; the sy l l a buses of a l l the maj or Examination
Boards ha ve be en ta ke n into ac coun t a nd que s t i o ns s et by th ese bo ards have been
i nc l ude d.

Al th o ugh ILPAC was i nitiall y conce ive d as a way of ove rc omi ng some of the
d iff iculti e s pr e sent ed by u neconomica l ly sma l l s i xth form s , it has fr eq ue nt ly
been ad opted because i t s ap pro a ch t o l ea r ni ng has ce r t a i n advantages over more
t radit iona l teac hing me th ods . Stud e nt s assume a g reate r r e sponsibility for
t he i r own l earning and c a n work , t o some ext e nt , a t thei r own pace , whi l e
t eac hers can devote more time to gu i di ng individu al s t ude nts and to managing
reso urc es .

By pr ov id ing pe r sona l gu idance , and de t a i l ed s o l ut i o ns t o t he many e xercis es ,

su ppo r ted by th e optio nal use of vi d eo- cas set t es , t he Pro j ec t allow s students
to study A-level c hemis try wi t h l e s s t eac h er - c o nt act ti me t ha n a conventional
cours e dema nds . The ex te nt to whic h thi s i s possible mu s t be determined
locall y; po ten tiall y haza rdous pra ct i ca l work must , of cou r s e , be s upe r Vi s ed .
Neve rthe less , fle xi bilit y in time-tabling makes ILPAC an attract ive propo-
sition in situations where cl a ss es are small or suit ab l y- qualified teach ers
are s carce .

In additi on , I LPAC can provi de at least a parti al so l ut io n t o ot her pro blems .

Students with only limited ac c e ss t o laboratories, f or e xample , those studying
at evening classes , can c o nc e nt r a te upon ILPAC prac tical wor k in the la bor a t or y,
in the confide nce that r e la t e d t heo ry c a n be s ystemati c al ly studi ed elsewhere .
Teachers of A- level chemistry who a re ine xp erienced, or whose main discipl ine
i s another science , wi ll f i nd I LPAC ver y supportive. The ma t e r i a l s can be used
e f fectivel y where upp er and lower s ixth f orm class es are ti metabled together .
ILPAC can prOVide ' r eme di a l ' mat e r i a l for students in hig he r education .
Schools operating s i xth form consortia ca n bene fit from t he cohesion t hat I LPAC
can provide in a f r a gme nte d situation . The pro ject can be adapted for use in
parts of the wor ld where th ere is a severe sho rtage o f qualified chemistry
teachers . And so on .

A more d e t ai l e d introduction to ILPAC , with spec ific advice both to stude nts
and to teach ers , i s included i n the f i r s t volume onl y . De t a i l s of the Project
Team and Trial School s appear inside the back cover .

LONDON 1983

v
ACKNOWLEDGEr~ENTS

Tha nks are du e to the fo llowing exami na tion boards f or pe r mi ss i o n to

reproduce que st i o ns f r om past A-le vel papers:

South ern Universities Joint Board;

Leve l One Test 3( 1975)

Oxf o r d Del eg ac y of Loca l Exami na tio ns;

Exerci s e 33(1 978 )

The As socia ted Exa mi ning Board;

Le ve l One Test 2( 1980 )

Univ ersity of London Entran ce and Sc hoo l Exa mination s Co unc i l ;

Teach er-mar ked Exerci s e s, p40(L 1978), p7B(N1976 )
Exercis es 4 5 ( N19 75 ) , 59(N1979 ), 61(N19n)
End-o f-Unit Test 1(N19 75 ), 2( L197B l, 3 ( N19 79) , 4( L19771 , 5(L19 BO)
6[N 1978 l, 7(N19 78 l, 8[N1976 l, 10[ L1973 l, 11( L1 975)

Que st ion s f r om papers of other e xamini ng boa rds app ea r in ot her Un its .
Wh ere a nswers t o th ese que stio ns a re i nclu de d, th ey are pro vi ded by ILP AC
and not by the examination boards.

Photogra phs a r e incl uded by permis s io n as FoLl ows -:

Photogra phs of st udents - Tony Langham

vi
SYMBOLS USED IN ILPAC UNITS

& Rea ding Re vealing e xercises

~ Exerc ise ® Discussion

~\;l Test ~ Compute r programme

'A' Le vel question

~ Experi ment

' A ' Le ve l part qu estion

I I 00
Vi deo programme

[QU Film l oop

'A' Leve l ques tion
Spec i a l paper
Model - ma ki ng

Worked e xample

Teacher-marked e xercise

INTERNATIONAL HAZARD SYMBOLS

~ Harmful
~ Toxic ~i
...\i"~._ Radioactive
6 .,

[jJ Flammab le
tE Explosive

~
~
:. III Cor ro si ve Oxidising
~-

vii
INTRO DUCTION
In t his Un it you con ti nue yo ur s tudy of equil ibri um by a pp l yi ng th e
prin ci pl e s de ve l oped in Unit P2 t o eq ui l ib r i a i nvolvi ng wea k acids an d
wea k ba s e s , i nclu din g buffer so lut ions a nd i ndicat ors .

In Le ve l One we take a mainly qualitative a ppr oa c h , us ing the Br0 nsted-

Lowr y t he or y to def ine ac i d s a nd bas es , an d de f in i ng pH in terms of hydro ge n
i on concent ra tion . To e xpl ain the obs e r ved effe c ts of conce nt ra t i on and
di l ut i on on hydro gen i on c o nce nt r a t i on , we apply Le Cha te lier 's prin cipl e .
We di scu ss the acid dissociation constant a s a me asu re of t he strength of an
ac id a nd a ls o give an introd uc t ory ac count of buff er so l ut io ns .

Le vel Two cover s muc h the s ame mate r i a l but f r om a more ma thema t i c a l s tand -
poi nt . We a pply the equilibrium l aw t o systems i nvo l vi ng wea k acid s , weak
base s , buffer s ol ut i o ns a nd indi c ators ; in each type of sys te m th e funda-
ment a l pr in cipl es a re the same . Our disc u ss ion i nclud e s t he wa y i n which
pH change s durin g diffe r en t t yp e s of a c i d- ba se t i trati on , a nd t he c hoic e of
indi c ators for such titra tions .

There are e ig ht ex pe r i me nt s i ~ t hi s Un i t , th ree in Le ve l One an d f ive i n

Leve l Two ; th e f i r s t thre e are ve r y s hort , but you ma y not ha ve time t o do
all th e oth ers .

PRE-KNOWLEDGE
Befo r e you s tar t work on t hi s Uni t , you shou ld be abl e to :

(1) app ly Le Cha te l ie r 1s pri ncip le t o s ys t ems i n eq ui l i br ium ;

( 2) ap pl y th e eq Ui l i br i um l a w to an y reversibl e pro cess by wr i t i ng an
expression fo r t he equilibrium constant ;
(3 ) do simple cal cul a ti on s of r e actin g ma s s based on given c he mic al
e q ua t i o ns ;
(4) write ionic eq uat ion s from f ull eq uat io ns , and vice versa ;
( 5) solve a qua dratic equ ati o n .

PRE-TEST
To find out whether you a r e re ady to start Le vel One, try the
f o l l owi ng test , whi ch i s ba s ed on the pr e - knowl edg e it ems . Yo u
should no t sp e nd mo re th an 30 minut es on t hi s t est . Ha nd you r
a ns wer s to your teacher for ma r ki ng .

1
PRE-TEST
1. Consider the equ i librium system :
Br2(aq) + H2Q(1 ) ~ H+(aq) + Br-(aq) + HBrO -(aq )
Use Le Chatelier 's pr i nc i pl e to answer the following ques tions .
(a) What effect would passing hydrogen ch loride gas in to the mixture
have on the pos ition of equili brium? (2 )
(b) What effect would addi ng so lid so dium hydroxi de ha v e on th e
concentration of bromine? (2 )

2. For eac h of th e fo llowing reactions , wr ite an e xpression for Kc .

Work out uni t s fo r Kc and inc lude them in your answers . assumi ng
concentrations a re meas ured i n mo l dm- 3 •
(a ) 2NO(g ) -->.
~ N2 ( g ) + ° 2(g ) (1)
(b ) 2S0 2(g ) + ° 2( g ) ~ 2S0 3 (g ) (1)
( c) CH 3C0 2H(aq ) + H2O(1) ~ CH 3 CO 2 - ( aq ) + H30 +( aq ) (1)
(d) H2O( l) ~ W ( aq ) + OH-( aq ) (1)

3. So lve the fo llow ing equation fo r x

x 2 = (1 .5 x 10 -~) - (1 . 35 x 10 - 4)x (4 )

4. Hydrochloric acid and calcium hydroxid e r e a c t toget her according to

the fol lowi ng eq uation :
Ca (OH) 2(s) + 2HCl(aq) ~ CaC1 2(a q) + 2H20( 1 )
3
What mass of Ca(OH)2 reacts with 25 cm of 0 .25 M HCl? ( 4)

(Ca = 40, ° = 16 , H = 1 . 0)

5. Wr ite ionic equations for the f oll owing reactions :

(a) NaCl (aq) + AgN0 3 (aq) ~ AgCl( s ) + NaN03(aq) (1)

(b) NaOH( aq) + HN0 3(aq) ~ NaN03( a q ) + H2°(l) (1)

(c) H2S0 4 (aq) + BaC1 2(aq) ~ BaS0 4(s) + 2HCl(aq) (1)

(d) 2HCl( aq) + K2C0 3(aq) ~ 2KCl( e q l + H20( 1 ) + CO 2(g) (1)

( Tota l 20 marks )

3
LEVEL ONE
I n the f irst two sect ions of t his Unit , we taK e a more de ta iled l OOK a t a cids
an d base s and show t ha t t he i r r e a c t i o n s in so l ut ion ar e equi lib r ia in whi ch
hyd r oge n ion s a re transf err ed f r o m a c i d s to ba s e s . To s tar t wit h , we f ocu s
on t he hydr o ge n i on itse lf and its be hav io ur i n a qu eo us so lut ion .

HYDROGEN IONS

Object ives . Whe n you ha ve f in is hed t his sect io n, yo u sho uld be a bl e t o :

(1 ) id en tif y the hydrogen i on, H+, a s a pr o t o n a nd fu ndament al pa rt i c le ,

with v ery diff e re nt properties f r om ot he r po s it ive ion s ;
( 2) demonstrate how th e hi gh ch arg e densi t y of t he hydrog e n ion aff ec t s it s
be hav i o ur ;
(3) writ e a n equati on for t he format ion of the hyd ra ted prot on , H30 · ,
some times call ed th e h ydro nium , o xonium or hydro xo nium ion ;
(4 ) i dentif y s ubstances that wi l l be at t ract ed to a pr o t o n a nd bond wit h
it .

Size of hyd rogen ions

Hydro gen is th e s ma l l es t atom , cons ist i ng o f on e pro ton and on e e lect r on o nly .
Whe n it ioni z e s , a s ingl e proton i s le ft :
H( g ) .... W ( g) + e-
In o t he r wo r ds , t he hydro gen i on i s a bare pr oto n , a fu ndamen ta l part ic le .

The d iame t er of a pro ton i s a bo ut 10- 1 5 m, whi c h i s a bo ut 100 , 000 times

smal le r th a n t he ne xt large s t pos i t i v e i on, the l i t h ium io n . Thi s mean s t ha t
it ha s a hi g h s ur f ace cha r ge de ns i t y *, which maKes i t a powe r fu l c e nt re of
posi ti ve cha r g e . A pr oto n is t he re f or e s trongl y a t t ra c t ed by an y ne ga ti ve
i o n or mol ecu l e whi c h has o ne o r mor e un sh a r e d e l e c t ro n pai r s .

*The s urfa c e c ha r ge de ns it y ca n be thou g ht of a s charge/s urfa ce a rea . A

prot o n has a ver y hi gh s ur f a c e ch ar ge d ensi t y be ca use its s urfac e a re a i s
so sma l l . The g r e a t e r t he surface char ge d e ns ity o f a n i o n , t he gr eater i s
t he el ect r i c f i eld i t g e ne r a t e s a nd t he g r e a t e r i t s po lar iz ing power .

Hyd rogen ions in solution

Bare pro tons a r e not found i n wat er . Because of their sma l l s ize and hi g h
char ge t he y a re a lway s bo nded to at l e a s t on e water mol ec ul e. The e ne rg y
cha nge t hat ta Kes pl ace whe n a proto n i s hyd ra t ed i s ve ry fa vo ura ble :
6H~
hyd = -10 75 KJ mol - 1

5
Compare this valu e wi t h the s ta nda r d h ea t of hydration of a li thiu m ion :
Li +( g) + aq ~ Li +(aq) ; 6Hhyd -499 . 1 kJ mol-~

The first s t e p in the hydration of a pr ot o n is the form ati on of a hydroniu m

ion* , H30 +. One of t he uns hared e l e c t ro n pa irs o n th e oxygen atom of a wa t er
mole cul e makes a da tiv e c ova le nt bond with a proton .

·S everal t erms e x is t f or the na me of H3 0 ' . We wi l l u se 'h yd r oniu m i on ' s i nc e

' hydr oxoni um io n ' a nd ' oxon i um ion ' giv e a mi s l eadi ng idea of i t s compositio n .

To c he c k that yo u know how th e e lec t r ons would r earra nge in t his r e a cti on,
tr y t his short e xercise .

Exerci se 1 (a ) Using d ot-a nd-c r os s di a gra ms , s how t he fo r ma tion

of a hyd ronium i on f rom a wate r mol e cul e a nd a
pr o to n .
(b ) Ac count for t he shape of t he hydronium i on .
(Answers on pa ge 91 )

Hydro nium ion s were f i rs t ide nt i fie d

in 1924 by X- r a y c r yst al lography of +
c h l o r ic ( VI I ) ac i d-1 - water , HC I0 4 'H20
( s hown t o conta i n H3 0 + an d CI0 4 - ) .
Since then , fu rthe r work ha s bee n
~@
... 0 .

do ne , in cludin g diffraction s t udi e s . H" :' H :' ..,

'.'.. .•'.•... H
:
......... : ..
o n differen t co nce ntra t io ns of
hydro chlori c ac i d s o l ut io ns ,
c onf i rmi ng that hydroni um i on s ar e
a l so pr e s e nt i n a q ue o us s o l ut i ons . Fig . 1. The hydron ium ion

Further hydration of H30+

The hydron ium ion too ha s a powe rful e l ectr ic fi e ld arou nd it and a t t r act s
mo re wa t e r mol ecu les to i t s el f. The e nerg y change i s , of c o urs e , s ma l l e r
th a n that f o r hydr a t ion of a proton :
H3 0+(g ) + aq ~ H3 0 +(a q ) ; 6H~ = - 4 18 kJ mo l - ~

I t s hydrat io n ene r gy i s s i mi l a r to tha t of other ga s e ous met al ca t i ons ,

espec ia l l y t he sodi um i on, wi th whi c h t he hyd ro ni um i o n is iso e l e c t ronic :
Na +(g) + aq ~ Na +( aq ) ; 6H ~ = -406 kJ mo l - ~

In t he p r o ce s s of hydratio n , ad di tio nal wat er mo le cu l e s arra nge t hems e l ve s

a r o und t he hydronium i on . The numb er va r i e s a cco r di ng t o bo th t h e conc en -
trat i on of hyd r ogen io ns and th e te mp erat ure of t he solut io n . The fol lowi ng
s pe c i e s ha ve bee n i de nt if i ed :

Ex erc i s e 2 How ma ny ad d ition al wate r mo l ecul es su rro u nd th e

c e nt ra l hyd ro ni um ion in e a c h of t he a bove formul a e?
( Answe r on pag e 91 )

6
Attraction of hydrogen ions by other centres of negative charge
In an y aqueous so lution , hyd ron i um ions and wate r mo l e c ul e s a re in a state of
dyn a mic equilib riu m. If we co uld trac e th e pa th of a part i cu la r proto n , we
would find th a t i t wa s con t i nua l l y movi ng from on e wa t e r mo le cu le to a nother :
H30 +(aq) + H, OC I ) ~ H,O( I ) + H30 +(aq)
<, w.----/
Wa te r mo l ec ules are not t he only part i c les to att rac t protons . The ne gat i ve l y
ch a rged part of a ny po l a r mo lecu l e , or a ny ne gati ve io n , att ra ct s a proton
an d , gi ven the r i ght con diti ons , ma y bond wi t h i t . Suc h s pec ies are ca l l ed
' ba s e s'.

Fo r e xa mpl e , s uppose that ammon i a i s b ubbl e d in t o a n a c i d s o lut io n . As s oon

as a n ammo ni a molecu le e nt e rs th e s olution , its un s hared pa i r of el ectron s
at t ra c t s a prot on fr om a ne ighbou r i ng hydron i um ion . The bond betwe e n t he
proton a nd th e water mol ec ul e wea Kens a nd a new bo nd f o r ms betwee n the pr ot o n
a nd the ammo ni a mo l ec ule . We i ll ustra t e t hi s in Fi g . 2 .

+ +

Fig. 2. The react ion between hydron ium ion and ammon ia

The re i s , in effe c t , a compet it i on be twee n ammo nia an d water fo r t he pro t on .

Beca us e the prot on ha s bee n t r an sferred f r om the wat er t o th e a mmo ni a , we sa y
t hat ammon ia i s a s t r onge r ba s e than wa te r . We normal l y wr i t e th e eq uatio n :
NH3 ( a q ) + H3 0 +Ca q )
NH4 +Caq ) + H, O( I )
~

9
Kc for th i s r ea ction i s 1 .8 x 10 • Thi s to o te l l s us tha t a mmo ni a i s a
s t r o nge r ba s e t ha n water , bec a us e t he equ i l i br i um l i e s s o f a r t o th e r i ght .

To s how t ha t you ca n r ec ogni s e ba ses , an d wr i te e qua t i on s f or t heir re a c t io ns

with hydr oni um i ons , t r y t he ne xt e xe r cis e .

Exe r cise 3 Wh i ch of th e f o l lowi ng s pec i es can a c t a s a bas e i n

a queo us so lu t io n? Wr i te a n equa t io n fo r ea ch r ea ction
t ha t c oul d taKe pl a c e wi th hydro ni um i on s .
(a) OH-( a q ) ( c) Na +( a q )
( b) C0 3 ' - (aq ) (d ) S0 4' - Caq )
( Ans wers on pa ge 91 )

Thi s i dea of pr o to n t r a nsfer i s th e bas i s of t he Br 0ns t e d - Lowr y theo r y of

a cids an d ba ses , whi ch you st udy i n the nex t se ct io n .

7
THE BR0NSTED- LOW
RYTHEORY
Thi s t he o ry us e s the id ea of proton tra nsfer to exp la i n t he be ha v io ur of
ac i ds and ba s es in s o l ut i on . I n yo ur s t udy you ap pl y t he theo ry t o aq ueou s
sol ut ions , but on e of it s advantage s is t hat i t can a lso be appli ed t o some
so l ut i o ns where t he sol ven t is not wa t er .

Obj ectiv es . Whe n yo u ha ve fini s hed this s ectio n , yo u s ho uld be a bl e to:

(5 ) define a n a c id a nd a base in te rms of t he Br0nsted -Lowry t he ory;

( 6) def i ne a con j uga t e aci d-ba s e pai r a nd be ab l e to ident ify the conjugat e
base a nd conju gate aci d in s uc h a pair ;
( 7) def i ne a s ubst a nce as an acid or a ba se a c cordin g to it s behav io ur in
gi ve n circumstances;
( 8) de f i ne a n amphiprotic s ubsta nc e as one whi ch can beha ve bo th as a n ac id
and a s a base in dif f erent s i t uat i o ns .

Sta rt by r ea din g ab out t he Br 0 ns t ed - Low ry the o ry of a c id s and ba s es,

whi ch wi l l g i ve you the d ef in itio ns . Loo k in the i nd e x, und er e i ther o
' Br o ns t ed ' or ' Lowr y' or ' a c i ds - a s pr ot on donors ' . Q]
Exe rcise 4 In t erms of the Br 0 ns t ed - Lowr y theory , define
(a ) an ac i d , (b) a ba s e.
( Answers o n page 91 )

As you have just lea rn ed , a cids and bases are r elate d by th e i r a bi l it y t o

do nat e or acc ep t prot ons . Thi s lea ds t o t he idea o f co njugate ac id -ba se
pa i rs , which yo u co nsi de r next .

Conjugate acid ~base pa irs

The i mportant st e p in any ac i d - ba s e r eaction is pr oto n tran s f er . An aci d
g i ve s up a proto n t o a bas e which acc e pt s it. In t he process , t he ac id
i ts el f become s a bas e , th e c onj uga te bas e of the a c id , a nd t he base bec omes
i t s co nj ugat e ac i d .

An ex ampl e wil l make this clearer . Wh en ethanoic aci d i s adde d to water,

some of the acid molecule s ion i ze in s ol ut io n . Each molecule that ion izes
los es a proton to bec ome it s conju gat e base , th e e t ha noa t e i o n:
CH3C o Z- ( aq) + H+
CONJUGATE BAS E + PROTON
This pr ot on i s acc ep ted by wat e r , a cti ng as a base , f o rmi ng it s con jugat e
ac id , t he hydron ium io n :
Hz o (l) + H+ ~ H30 +(aq )
BA SE + PROTON ~ CONJUGAT E ACID

8
Addi ng t he s e tw o eq ua t io n s , a nd c a nc e ll i ng th e p rot o n whic h a ppea r s on b ot h
s ide s , g i ve s t h e e quat i o n :
CH 3C0 2H(a q ) + H2 0 ( 1 ~ ~ CH3C 0 2- ( aq ) + H30 ' ( a q )
ACID + BAS E ~ ACI D BASE +
1 2 2 1
In othe r words , t he re a re t wo c on j uga t e ac i d- ba se pa i r s i n th i s r e a c t io n :
ACIDS BASES
a nd
and

In ge n e r a l , an a c id a nd i t s co n juga t e b a s e d i f f e r on l y by on e p r o t o n . We
o f t e n u se t he form u la HA to r e p r e se nt a ge n e r a l acid ; its c o n j ug~te ba s e is
A- , a nd t h e e q ua t io n r e l a ti n g trle r.l c a n be wr i tten :
HA ~ A- + W

Howeve r , t h i s r e ac t io n o n ly takes pl a ce i n th e pres e nc e o f a se cond ac i d -

ba s e pair ; i . e . a c corn i ng t o the Br0n s t e d - Lowry t heo r y , an ac id is o n ly
a n ac i d i n t he pre sen c e o f a base,a nd a ba se i s onl y a b a se in t he pre s enc e
o f an ac i d . I n t he ne x t e xerc ise , y o u i d e ntif y c o n juga te a c i d - ba se pa irs .

Ex ercis e 5 Ide nt if y th e co n j uga t e pa irs i n e ac h o f t h e f o l l OWi ng

r e a c t i o n s:
(a ) NH 3 (a q ) + H2 0 ( 1) ~ NH 4 • (a q ) + OH-( a q )
(b ) HN03( a q ) + OH-(aq ) ~
~ N0 3 - ( aq ) + H2 O( 1 )
( c) H2 ° (l ) + H2 ° (l ) ~ H3 0 '( aq ) + OH-( aq )
(d ) HS0 3 - (aq ) + H2 O( 1 ) ~ S0 3 2 -(aq ) + H3 O'( aq )
(An s wers on pag e 91 )

Fo r co nv e n i en c e , we o f t en wr i t e I H' ( a q)1 a s a shor thand f o r m o f ' H3 0' ( a q ) I;

t he t wo f ormul a e a r e i nt e rch an gea b l e in mo s t c a s e s . Th is me a n s t ha t any
e qua t i on yo u s e e wr i t t en wi th ' H' ( a q )' ha s an e q Uiv a lent for m wit h I H~ O ' ( a q )1
an d v ice ve r s a . In th e fo l l owing e x erc i se s , yo u c onve r t o n e f o r m to t h e
ot he r ; r e me mb e r to ba l a nce t h e e q ua t ion s b y a d j u s ti ng t h e a mo u n t of wate r
i ncl ud e d .

Exe r c ise 6 Rewri t e these equat io ns i n a fo rm us i ng ' H' (a q) ' :

(a ) NH3 ( a q ) + H 30 ~ (aq ) ~ NH 4 '( a q) + H20 ( 1)
(b) H2C0 3(aq) + H20 ( 1 ) ~ HC0 3 - (a q ) + H3 0 ' ( a q)
(c) BaLDH) 2 ( s ) + 2H 30 ' (a q ) ~ Ba 2 '(aq ) + 4H2 0 ( 1 )
(Answ e r s on pa ge 91 )

Ex e r c i se 7 Re wr ite t h e s e e q ua t io n s i n a fo rm us ing ' H3 O' ( a q )':

(a ) HN0 3 ( a q ) ~ W (a q ) + N0 3 -( aq)
(b) HC0 2H(aq ) <= W ( a q) + HC0 2 - ( a q )
(c ) 'l2 S0 4 ( aq ) <= H"( a q ) + HS0 4 - ( a q )
(A n s we r s o n pa g e 91 )

9
The majorit y of th e a c id -base rea ction s that yo u s t udy entail the transfer of
a r r ot on t o or from a wate r mo lec ule :
H20( 1) + ACID ~ H3 0+ ( a q ) + CONJUGATE BA SE
H2 0 ( 1 ) + BASE ~ OH-(aq ) + CONJ UGATE ACID
This is why yo u ha ve been a ccustomed, i n pre-A - leve l wo r k, to linking aci ds
with hydro gen ion s , and base s with hydro xide ions . In the follow in g e xerci s es
you wri te equation s to show how a number of substances can be ha ve as a c i d s
or ba s e s i n aq ueo us so l ut ion .

Exerci s e 8 The fo l lowing s ubsta nces beha ve as bases in aqu eous

s olu tion . Write a n equa t ion fo r each on e t o show how
it s c o nj ugat e acid i s f or med .

( a) OW(a q) (b ) HS0 3 - (aq ) ( c) H2 0 (1 )

(d ) C03 2 -(aq ) (e) HC0 3 -(aq )
(Answers o n page 91 )

Exerci s e 9 The f ollowing s ubsta nces beh a ve a s ac i ds in s ome ~

c irc umsta nces . For each o ne , wr ite an equatio n to show
t he fo rma t i o n of i t s co nj ugate base: ~\

( a) HC0 2H(aq) (b ) H2 0 ( 1 )
(d ) H2 S(aq ) ( e) HS0 3 - ( aq l
(Answers o n page 91

Remembe r that the Br0nsted- Lowr y defi ni t ion he lps us to recogn ise acid -ba s e
behavio ur . It does no t ca tego r i s e s ubst a nc e s as acids or bas e s , but give s
us a way of dec id ing , i n a ny g i ve n situatio n, whether a subst ance i s a c t i ng
a s an ac i d o r a base .

For example , i n Exe r ci s e 8, the hydrog en su l phite i o n, HS03 - , is s hown act i ng

as a ba s e, but i n Exerc ise 9 , i t i s s hown a ct i ng as an acid :
HS0 3 - ( aq ) + H+( a q) ~ H2 S0 3( a q )
HS0 3 - ( aq ) ? H+( aq ) + S03 2 - Caq)

Exerci s e 10 Loo k a ga in at you r a nswe rs to Exerci s es 8 and 9 .

( a) Fin d the substances , a part f r om the hydro g en-
su lphit e i on , which can act as e i t he r Br 0n sted -
Lowry acid s or bases acco rdi ng to ci rcums ta nce s .
( b) Summa r i se you r a nswe r s to Exerc ises 8 a nd 9 by wr iti ng a
ge ne ra l s ta temen t a bout the wa y i n whic h acids and bases
t en d t o re a ct in aqueo us sol utio ns .
( Ans we r s on pa ge 91 )

Subs t a nc e s whic h c a n be ha ve e it her as Br0nst ed- Low ry acids o r bases acc o rd i ng

t o circumstances ar e ca l led a mphipro t i c .

10
Amphiprotic substances

IAmphi - 1 c omes f r om the Gre ek , meaning Io n both s id e s ' an d ' pr o t i c' refers
t o proto ns , so amphi prot ic substances fi t bot h Br 0n s t ed - Lowry defi nit io ns
and c an gi ve up as well as re ce i ve pr oto ns .

Certa i n s ubsta nc e s are no rmal ly a mp hi pro ti c in aqu e ou s so lut i on . e . g . wat er

itself ; others c an be amphi pro ti c in di f f ere nt s olve nts , e .g . ammonia .

Now try th e ne xt e xerci se t o show t ha t yo u ca n r ec o gni s e s ome a mphi pr ot i c

s ubs t a nc e s in addit io n t o those mentio ne d i n Exerc i se 10 (a ) .

Exe rc i se 11 De cid e which of t he f oll owing are nor mall y amphi protic
i n aq ue ous sol uti on . Wri t e eq ua t i o ns to expla i n yo ur
a nswe r .
( b) HN0 3
*H2C20 4 , someti me s wr i t te n ( C0 2 H) 2 ' i s t he dibasic carb o xy l ic
acid , ethanedi oi c a cid (o xa lic acid) .
(Answers o n pag e 92 )

I n th e next exe rc ise the s ol vent i s not ne c e s s aril y wat er .

Exerc i se 12 (a) Use yo ur knowl e dge of the Br0n s t e d-Lowr y t heo ry

to i dentif y th e base i n e a c h reac tion :
(i) HS0 4 - + HN0 2 ~ H2 N0 2 + + S0 4 2 -
(ii )

( i ii ) CH3 C02 H + HN0 3 ~ CH3C 0 2H2 + + N0 3 -

(iv) HBr + HCl ~ Br - + H2C l +

(b ) Expl ain why a mixt ure of pure ni tric a ci d ( HN0 3 ) a nd pure
c hloric(VI I ) aci d ( HCI 0 4 ) c on ta ins H2 N0 3+ ion s a nd CI0 4 -
ions .
(Answers on pa ge 92)

We have a l r ea dy referred , i n pas s i ng , to th e i o ni zat i on of wate r ; now we

consi d er i t i n mor e deta i l .

11
IONIZATION OF WATER
Object i ve s . When you have f i ni shed this section , you should be a bl e to :

(g ) write an equ ati on f o r the se lf - i oni zation of water ;

( 10 ) de r ive the exp res sion for K , th e ioni c pr oduc t of wat er ;
w
( 1 1) def ine ac id ic , neu t ral a nd ba s i c solutio ns in terms of their hyd r ogen
io n c oncent ra t i on;
(1 2) us e th e i oni c pr oduc t of wate r t o calc ula te the co nc e nt r a t i o n of
hyd ro xide i on i n a so lut ion of known hyd roge n i on con c entration .

Rea d a bo ut t he ioni zati on of water in your t ext -boo kC s). Yo ur

re ading will help you wit h th e s ec tion s wh i ch fo llow.

Wa te r is a spe cial case of an amphi pr ot i c su bstance ; it ca n react with

i t s e lf :

The evidence t ha t thi s proces s ta ke s plac e i n ev en th e pur e s t wat er i s that

it has a slight elect rical conductivity . A few ions must be pr e s e nt to carry
a cu rrent a nd these must have c ome from the io nization of the wa t er molecul e s
t hemselves . A s i mpl er way of writin g the eq uatio n is :
H20 CI ) ~ H+( aq) + OH-Caq )
In the ne xt two exerci ses you fi nd ou t mo re about thi s equil ibrium.

Exe r c i s e 13 Kc f or t he equa t i o n i s 1 . 80 10- 1 6 mo l dm- 3 a t 25 ° C.

X ~
From your know ledge of the ma gnitude of Kc va lues, in
wh ich di re cti o n does th e eq uilib ri um lie ? ~\

(Ans we r on pa ge 92 )

Exercis e 14 I n pure water a t 25 °C , th e eq ui l ibri um co nc ent r at io n ~

of un -ioni z ed wa t e r mol ec ul es is 55 .6 mol dm- 3 •
Gi ven t hat Kc i s 1 .80 X 10 - 1 6 mo l dm- 3 , cal culate th e ~~
f r a cti o n of wate r mo lecu les ioni zed at thi s t empera ture .
(Hint : c a lc ul a t e [ W Ca q J] and [ OH-Ca q J] firs L)
(Answer on page 92 )

The ionic product of water

We de r i ve t he expres s i o n for the i on i c product of water , Kw' f rom t he

e quil ibri um law ex pression f or t he s e lf - io ni za tion of wate r :
H20C l ) ~ H+Caq) + OH-Caq )
[H +C aq) ] [ OH-Caq )]
K
c [ H2 0Cl i

12
So f ew wa t er mol ecul es a re ioni z ed tha t t hei r c onc e nt r a t i o n r ema ins ef fec -
tive ly con st an t (p r o port i on al to the de nsi t y of wate r ) . We can the refo re
include [ H2 O(1 ) ] with the c o ns t a nt K .
c
Kc x [ H20(1 ) ] = [ H+(aq ) ] [ OH-C aq) ]
Let Kc x [ H2 0 (1 ) ] be a not her const a nt , K
w
IKw [ W Caq)] [OH-Ca q)] I
This ex pr es s i o n i s known a s t he ionic produc t of wa ter . In yo ur r e a di ng
you may als o s e e it wri tt en i n th e f orm :
K = [H30 +(aq) ] [ OH- Caq ) ]
w
Thi s mea ns th e s ame a nd c a n be used i n exa c t l y the same way as the above
e xpres s i on; its only diff ere nce i s that i t has been derived usin g the ' f ul l '
eq uation f or th e io ni z a t i o n of wa t er :
H2O(1) + H2O(1) ~ H3 0 +Ca q ) + OH-C a q)
The va l ue of the io nic pro duc t ha s bee n measured exper i me nt al ly a nd foun d t o
be 1 .0 x 10- 1 4 mo1 2 dm- 6 a t 25 °C . Si nc e it is direc tl y r el ated t o th e
equilibrium con stant f or th e s e l f- i o ni za t i on of wat e r , this value is , of
cou rse , tempera tu r e depende nt .

The aim of the f ollowing Reveali ng Exerc ise is to ex a mi ne what ha ppe ns

when th e equ ilibrium i n pure wate r i s ups et by t he ad dition of
hyd rogen i ons f rom an acid or hydro xi de i on s f rom a n alkal i . Also ,
s i nce Kw is constant , we der i ve a defin i tion of a cid ic , ne utra l a nd
ba s i c sol utio ns i n t erms of t he con c e nt r a t i o n of hydro gen ions .

Cons id e r th e eq ui lib r i um :
H2O (1 ) ~ H+(aq ) + OH -Caq) ; Kw = 1 .0 X 10- 1 4 mo1 2 dm- 6
01 . Ca l c ul a te [ H+ ( a q ) ] a nd [OH- ( a q ) ) in pure water.

A1 . Kw = [ H+( a q) ] [ OH-( a q ) ] = 1 .0 X 10- 1 4 mo1 2 dm- 6

Since [H+( a q ) ] = [ OH- ( aq) ] , the n
[ H+(a q ) ] 2 = 1 .0 x 10- 1 4 mo1 2 dm- 6
:. [W(a q)] 1 1 .0 x 10 14 mo1 2 dm 6 1 .0 x 10- 7 mol dm- 3
an d [OH-(aq )] = 1 .0 x 10- 7 mol dm-3

02 . Acid i s added to t he so lut ion to increa s e t he c on c en t ra tion of hydro ge n

i ons . How doe s t he equi li brium shift?

A2. It shifts t o the l eft .

03 . I s the co nc e ntra t i on of hydr ox i de io ns le ss than or gr eate r th a n

1 .0 x 10- 7 mol dm- 3 now?

A3 . I t i s l es s t han 1 . 0 x 10 - 7 mol dm- 3 •

04 . Do e s t he co nce ntra tio n of hydroxid e i ons ever decrease t o z er o ? Expl ain .

13
A4 . No . The i o ni za t i on of wa t e r i s an eqUilibri um s ystem . The produc t of
c onc e nt r a t i o ns of hydr ogen i ons a nd hy dro xi de i o ns must alwa ys be
1 . 0 x 1 0 - ~ 4 mo1 2 dm- 6 • The onl y way f or on e va l ue to drop t o z e r o
wo ul d be f o r the ot her to be i nf in ity , which i s i mpo s s ibl e.

05 . Wha t is t he eff ect of a ddi ng a l ka l i t o t he equilibrium syst em ex i s t i ng

in pure wat er?

AS . It shif ts t he eq ui l ib r ium to th e left .

06 . I s t he co nce nt r at io n of hydroge n io ns gr ea t e r than or less than

1 .0 x 10- 7 mo l dm- 3 now?

A6 . I t i s l ess t ha n 1 .0 x 10- 7 mo l dm- 3 •

07 . Does the hydr og e n i on co nc e nt r a t io n ev er decreas e t o z e r o ? Exp l ain .

A7 . No , for simil ar r easons to t ho s e g i ve n in A4 .

To s umma r i s e , i n a ne utral so l ut i on ,
[H+( aqJ ] [ OH-( aq ) ]
[ H+( a q J ] [ OH-(aqJ]
In a n ac i d i c so l ut io n,
[H+(aql ] > [ OH-( a q l ]
a nd [ H+(aq l ] > 1 .0 x 10 - 7 mol dm- 3
I n a bas ic , or a l kal ine , so l utio n ,
[H +( aq l] < [ OH- ( a q J]
and [ H+(a qJ ] < 1 . 0 X 10 - 7 mo l dm- 3

Using the expression for t he ionic product of wate r

Si nce th e pr odu ct of co nce ntra t ion s of hydrogen i ons an d hydroxid e io ns is
al ways co ns ta nt for an y di lut e s ol ution at a give n t empe r atu re , we ca n
ca l culate th e co nce nt rat io n of o ne of t hes e i on s gi ve n the co nc e nt ra t io n of
the o t he r . We s how you how to do t hi s in a Wor ked Exa mpl e .

Worked Exampl e Calcu lat e the hydro xi de ion co nce nt ra t io n in an

ac i d so l ut io n whi c h ha s a co nce nt ra t io n of hydroge n
ions of 0 . 10 mol dm-3 gi ve n t ha t
Kw 1 .0 x 10 - ~ 4 mo 1 2 dm- 6 at 25 ° C.

14
Sol ut i o n
1. Rea r r a ngi ng the expression :
Kw = [W(aq)] [OH-(aq)]
K
gives [Otr(aq)] = [W(:q ) ]
2. Subs t i t ut e the given val ues of Kw and [H+(aq)] ,

1 . 0 x 10- ~ 4 mo 12 dm -6
0 .10 mol dm 3 =
I1.0 X 10-~ 3 mo l dm- 3
I
Not i c e t ha t even in strongl y a c i d i c so lutio ns , there are hydro xide ions
pre sent .

Exercise 15 Give n that Kw = 1 .0 X 10 - ~ 4 mo 1 2 dm-6 , ca lc ulate the ~

hydroxid e ion concentratio ns of t he s e acid solut ions
at 25 °C . Assume that both a c i ds are full y dissociated ~\\
into io ns .
(a ) 0 . 010 M HC1
( Answers o n page 92 )

By rearranging th e e xpression f o r the io nic product of water to s o l ve for

[ H+ ( a q) ], you can calculate t he hydrogen i on co ncentration give n the
hydrox ide io n c once nt r a t i on .

Exe rcise 16 Given that Kw = 1 .0 X 10 - ~ 4 mo1 2 dm- 6 at 25°C ,

ca lcula te the hydrog en ion con ce ntrations of the
f oll owi ng so lutions . Assume t hat both al kalis are
f ul l y dissocia t ed in sol ution .
(a) 0 .010 M KOH (b) 0 .050 M Ba(OH)2
( An swers on pa ge 92 )

The effect of temperatu re on Kw

Yo u ' s houl d be able t o do t he follo wing exerci se by a ppl yi ng what yo u lea rned
in Uni t P2 about the effect of temperature change on equilibrium constants .

Exercise 17 The self- ionizatio n of water i s an endothermic process :

2H 20(1 ) ~ H30 +(aq ) + OH-(~q ) ; 6H~ = +6. 5 kJ mol - ~

Is the concentration of hydrogen io ns in pure water at

40 °C less th~n or greater than the value at 25 ° C?
Explain your answer .
(Answe r on page 92 )

In the ne xt s ect io n , we s how yo u how to ex pre ss t he concentra t i ons of

hydroge n i on and hydroxide ion more conve nient ly as pH .

15
 pH~ THE HYDROGEN ION EXPONENT
In t his s ec t io n yo u l earn what we mea n by pH. I n yo ur pre - A-le vel c o ur se
you us ed the pH sca le r a t her i nf orma l l y a s a meas ure of acidi ty wi tho ut
havi ng bee n give n a prec ise defin i tion . Yo u have dipp e d uni versal i ndica t o r
pape r into a so lu t io n t o f ind th e appro ximat e measure of i t s a c i d i ty a nd yo u
know t hat any solu t io n ha vi ng a pH above 7 i s alka line , while a s ol ut i o n
ha ving a pH below 7 i s a cid ic . In thi s sec t io n yo u l earn t he defi ni t i on of
pH a nd un derst and more f ul ly i t s s i g nific a nce .

Object ives . When you have f i nished t his section , you s ho uld be a b le t o :

( 13) def i ne pH;

(1 4) ca lcu la te pH fr om hydro gen io n co nce nt ra t io n ;
( 15 ) us e th e express i o n f or th e io nic pro duct of water to ca l CUl a t e pH
fr om hyd r o xi de i on co nce nt r a t i on ;
( 16) calcula te hydrogen ion con centrati on fr om pH.

Wh en we compare the ac idity o f di ffe re nt s ub st ances , we genera l ly tes t t he m

in water . This i s beca use s o ma ny ac id -ba se reac t i ons t a ke p l ace in aq ue ous
sol utio n th a t i t i s con ven ient to ' l i ne up ' ac i ds ac c ord i ng to t he ir abil ity
t o dona te a pr ot on t o wate r . For ex ampl e , cons ider any a cid , whi c h we
r e pr e s e nt as HA , d i s s o l v i ng i n wat e r an d io nizing .
HA( a q ) + H2 0 ~ H3 0 +(a q) + A-(aq )
or , HA( a q ) ~ H+( a q ) + A- (aq)
The gr ea t e r th e abil i t y of t he ac i d t o don at e proto ns to wate r , t he grea t er
t he co nc e nt r a t i o n of hydrog en io ns . I t would s e em lo gical , the refore , t o
compa re the s t re ngt hs of a cids by compa r i ng th e conc e nt r a t i ons of hydro ge n ions
prod uced in aq ueo us s ol ut i o n, a s shown i n Table 1 .
Tabl e 1

Sol ut io n [ W ( a q ) J/ mo1 dm- 3

A 0 .0010 = 1. 0 x 10- 3
B 0 .0000010 = 1. 0 x 10- 6
C 0 . 00000 000 10 = 1 .0 X 10- 51

Howeve r, a s cal e ba s ed on hydro gen ion c onc e nt rat io n co ntain s a wkward numb ers
a nd i s c umbersom e t o use .

16
 The Danish bioc he mist , S . P . L. S0 r e nse n ,
r eali s ed thi s a s ea r ly a s 1909 . He ha d
be e n working for Carlsber g on th e
problems conn ected wi t h the brewing of
bee r (in whi c h co nt r ol of acidi t y i s
i mporta ntJ . I t occurred t o hi m t ha t i t
was t ed i ous t o sa y ' t he co nc e ntra ti on
of hydrogen ion s i n t he so l ut io n i s
one-hun dre d- t hou sa ndt h of a mole per
c ubic decimetre ' when
[H +( a q J] = 0 .000010 mol dm- 3 (o r
1 .0 x 10- 5 mo l dm- 3 ) s o he su gge s te d
re fe r r i ng to t he s olu t ion a s ha v ing
' pH 5 ' .

As you ca n s ee , 5 i s the ne ga ti ve of the ' power of 10 ' in t he e xpress i on f or

hydr o ge n i on conce nt r a t io n ( I P I in •pHI s tands for I power ' ) . In ge nera l :

1 [ W ( a q ) ] = 1 .0 x 1o -pH I or , tak in g l ogari t hms, I pH = - lo g lo[W( aqJ] I

St r ic t l y spea ki ng , s i nce we can onl y t ak e th e l oga r it hm of a pure number,
we s hou l d write 10g lo([ H+( a qJ ] / mol dm- 3J b ut this prac t i c e i s not usuall y
ob s e r ved .

Use th e f i r s t of t he s e ex pr e ssi o ns in t he ne xt e xerci s e .

Exe r c i se 18 Wha t a re t h e pH va lue s for solut i ons A, Ba nd C i n

Table 1 o n page 16 ?
(Answer on pa ge 92 J

You sh ou l d ha ve s een fr om t he l ast exerc ise that , as t he con c ent r ati on of

hydroge n i ons i nc re ases , t he pH va lue decrea ses ; a nd , as t he concen t r at i on
of hydro ge n io ns decreases, the pH va l ue increa s e s .

Fig.3

We now show yo u how t o ca lcu late t he pH of f ul ly ioni z ed ac ids and al kal is

f rom th eir con c e nt r ati ons .

Wo rked Exampl e Wh at is the pH o f a 1 .0 M HCl solution?

So l ut i o n
Assu me t ha t thi s a cid is ful l y di s s ociated so t ha t the hydro ge n ion co nce n-
tra tion = 1 .0 mol dm- 3 •
Subs t i t ute t his va lue int o the ex pre ss i o n whic h def in es pH.

pH = - l og [W ( a q l ] = =lo g ( 1 . 0 ) '" - ( 0 ) =[Q]

17
 Now try the following exercise yourself.

Exercise 19 Calculate the pH of a 10 M HCl solution, assuming it

to be fully dissociated.
(Answer on page 92)

You have already made use of the ionic product of water to determine the
concentration of hydrogen ions in alkaline solution. Now we take you through
an exercise making use of the ionic product of water to calculate the pH of
an alkaline solution.

Worked Example What is the pH of a 1.0 M NaOH solution?

(Kw = 1.0 x 10- 1 4 mo1 2 dm-6 . )

Solution
Assume that NaOH is f ul l y dissociated in solution so that [OH-(aq)]
- 1 . 0 mol dm- 3 •
1. Starting with the ionic product of water, solve for [H'(aq) ]:
[H+(aq)] [OH-(aq)] = 1.0 x 10- 1 4 mo1 2 dm- 6
1.0 X 10- 1 4 mo1 2 dm- 6
[H''Leq l ] =
[OH l e q L]
2. Calcu:!.ate the hydrogen ion concentration:
1 0 x 10- 1 4 mo1 2 dm- 6
[H'T eq l ] • 1.0 mol dm 3 = 1.0 'x 10-1 4 mol dm- 3
3. Substitute this value into the definition of pH:
pH = -loglo[H+(aq)]
= -log r1.0 x 10- 1 4 ) - (0 - 14) = ~

Now try the following exercise yourself.

Exercise 20 What is the pH of a 10 M NaOH solution?

(Assume compl et e dissociation.)
(Answer on page 92)

The pH scale
The pH scale is usually taken to be between 0 and 14 even though pH values
of -1 and 15 are possible, as you saw in Exercises 19 and 20. Since we
rarely work with solutions much more concentrated than 1 M acid or alkali,
for most practical purposes pH = 0 is considered the lower limit and
pH = 14 is considered the upper limit of the scale.

18
The chart below shows the pH values of some co mmon mate rials .

14 1 .0 M NaOH

13 0 .1 M NaO H
I nc rea sing lime wa t er
ba s i c i ty 12
househol d ammonia
11 soap

10 milk of ma gnesia

9
baking soda
sea -water
8
blood
Neutra lity pH 7 pure water
milk
6 rai n-water

5 coffee
ba na na s
4 gr a pef r uit
apple s
3 vi neg a r
Increasing lemon juice
aci dit y 2
ga str i c jui ce
1 0 .10 M HC l

o battery acid

Fig .4. pH values of some common materials

The ne xt exe rcise is similar t o Exercise 20 .

Exercise 2 1 Calculate the pH , at 25 °c , of solutions i n which the

hydro xide ion conc e nt r a t i o ns are a s follo ws:
( al 1 . 0 x 10- 8 mo l dm- 3 (c ) 1 .0 x 10- 4 mo l dm- 3
(b) 0 .10 mol dm- 3
( Answer s on page 93

19
A s imple diagram f or summarls lng t he r el a t i o ns hi p between hydrogen ion
concen trat ion , hydrox ide io n c oncen t rat io n and pH (a t 25 ° C) wa s dev ised
s ome years ago by Professor H.N . Alyea of Princeton Uni versity , U.S .A . and
i s s hown her e in a mod i f i ed fo rm.

pH 0 2 3 4 5 6 7 8 9 10 11 12 13 14

[OH-(aq ll / mol dm - 3 10 - 1410 - 13 10 - 1210 - 1110 - 1010 - 9 10 - 8 10 - 7 10 - 6 10- 5 10 - 4 10- 3 10- 2 10- 1 10 0

Fig. 5. The relationship between [Hf Iaql ]. [OW(aq)] and pH

In ne utra l sol ution s at 25 ° C, [ H+(aq)] = [OH-(aq) ] = 1 x 10- 7 mo l dm- 3 •

However , as the conce ntration of one of them increases, the other must
dec rease accordingly . You can see this for yourself by placing a ruler
vert i c al l y a t any of the points indicated along the diagram ; you ca n a lso
deduce t hat [ H+(a q J] x [OH-(aq)] = 1 x 10- ~4 mo1 2 dm- 6 •

We now take you a step f ur ther i n pH calculat ions . For each calc ulation read
the' Wo rked Example, then t ry the exercises which fol low i t. If yo u are una bl e
to get the correct a nswers to these exercises , you may need to ask yo ur
teache r for he lp in t he us e of l oga ri t hms and ant ilogarithms . Also, for each
type of exe rcise there are addit ional exercises in Appendix 1 . They a re to
be us ed if you ne ed o r want more practice. If you a re able to do t he
exe r cises given , t hen do not do t hose in t he Appe nd ix un ti l yo u a re rev ising .

I n the f i rs t t y pe of prob lem , you calc ulate the pH of solutions where the
lo gari t hm of the hydrogen i o n concentra t ion is not a whole number . This is
rea l ly an exercise i n t he us e of l o ga r i t hms.

Calculating pH from hydrogen ion concentration

Wo rked Example Cal cul at e the pH of a so lut ion whose hyd rogen ion
conc e nt r a t io n is 4 .0 x 10- 3 mol dm- 3 •

So l utio n
Sub s t i tu te th e hydro ge n i on co nc ent ration i nto the expressi on :
pH -log [H '' Laq ) ]
pH - l og (4 x 10-3 ) - (-3 .00 + 0 .60 ) (- 2. 40) =~

Now try th e f o l l owing two e xerci s es. Of c o urse , i f you ha ve a s cie nt i fic
cal culato r, yo u ca n l et t he machine do the work .

20
Exerci se 22 Calcul ate th e pH of a s o lu t i o n whose hyd ro ge n i on
co ncen tration i s 7 . 0 x 10- 7 mol dm- 3 •
( Answe r on page 93 )

Exercis e 23 Cal cul a te t he pH of a s o l ut i on whos e hydr oge n i on

concent ration i s 3 . 2 x 10- 9 mo l dm - 3 •
(Answer o n pa ge 93 )

If you e xperienced any di f f i cult y with these c a lc ul ations , you ma y need help
wi t h the use of l ogarit hms ; ask you t e a c he r . There are s ome s imila r
e xe rci ses , fo r mor e pra cti ce or f or r evi si o n, in Ap pe ndi x 1A on page 85

Yo u ha ve a l r eady see n how t emperat ure ca n aff ec t t he i oni c pr od uct of wa t e r .

I n wor kin g t hro ugh t he f o llowi ng two exerc i ses , yo u l ea r n how t e mper a t ure
affect s the pH of pure water o r a ne ut ral s ol ut i on .

Exerc ise 24 Calcula te the pH of pur e wate r at 10 °C , at which

tem pe rature Kw = 0 . 30 X 10 - ~ 4 mo 1 2 dm- 6 •
(Ans wer o n pag e 93 )

Exercis e 25 Ca l cu lat e th e pH of pure wa t er a t 50 °C.

(Kw = 5 . 47 x 10- 1 4 mo 12 dm- 6 a t 50 °C . )
( Answer on pa ge 93 )

Now we t a ke yo u t hr oug h t he ca l c ul a t i o n of hyd roge n i on co nc e nt r a t i o n , g i v e n

the pH of the solut ion .

Calculating hydrogen ion concentration from pH

Worked Example Wha t i s th e hydro gen ion concentrat ion in a

s o l ut io n wit h a pH of 4 . 0 ?

Solu tion
1. Sub st i tu te t he pH va l ue i n t he e xpre ssi on :
pH = -log [H +(aq) ]
4 .0 = -l og [H +(aq )]
2. Rearra nge th is exp ress io n f or log [H +(a q )J :
log [ W(aqJ] = -4 .0
3. Ta ke the ant i l og :
[H +(aq )] = ant i log (-4 . 0 ) 11 . 0 X 10- 4 mo l dm- 3 I
Now t r y the fol lowing e xe rc i s e .

21
Exercise 26 Calculate the hydrogen ion concentration in solutions
with:
(a) pH = 9.0 ( b) pH 2.0
(Answers on page 93)

We now take you through a Worked Example where you are required to determine
the hydrogen ion concentration from a pH which is not a whole number.

Worked Example What is the hydrogen ion concentration of a solution

whose pH is 3.70?

Solution
1. Substitute in the expression:
pH = -log [H+(aq)]
3.70 = -log [H+(aq)]
2. Rearrange the expression for log [H~(aq)]

log [W(aqJ] = -3.70

3. Take antilogs:
[W(aq)] antilog (-3.70)
antilog (-4 + 0.30) = 12.0 x 10- 4 mol dm- 3 !
If you are using a calculator, refer to the instruction booklet.

Now try the following exercises yourself.

Exercise 27 Calculate the hydrogen ion concentration in a solution ~

which has a pH of 9.20.
(Answer 0 n page 93 ) ~\\

Exercise 28 Calculate the hydrogen ion concentration in a solution

which has a pH of 2.632.
(Answer on page 93)

If you experienced some difficulty with these exercises, you may need to ask
your teacher for help with the use of antilogarithms. There are some similar
exercises, for more practice or for revision, in Appendix 16 on page 85 .

So far, we have used pH as an indication of the strength of an acid.

However, pH varies with concentration so that, to compare the strengths of
different acids, we need another measure. This is the subject of the
following sections.

22
RELATIVE STRENGTHS OF ACIDS
Objectives. When you have finished this section, you s hould be a bl e to:

(1 7) demo ns t r a t e the effect of dilution on the pH of a cid s;

(18) differentiate between s trong an d weak acids on the basis
of the dilution effect;
(19) recognise that it is the val ue of the dissocia tion co nstant, Ka , and
not pH, whi ch provides a n a c c ura t e measure of rel ative acid strength;
(20) cal cula te the di ssocia tion constant, K a , f or an a cid f rom the
concentration of t he solu tion and its pH;
( 21) calculate t he pH give n t he di ssocia tion constant a nd concent r a t i o n of
a solut ion .

Consid er ag ain the equ atio n fo r the dis soci ation in wat e r of a general a cid
which we represent as HA.
HA( a q) ~ H+(a q ) + A- ( aq)
The further the pos ition of eq ui l ib r i um lies to the right, th e more hydrogen
i o ns are present and the stron ger the acid is consi dered to be.

Acids such as HCI, H2 S0 4 and HN0 3 a re c la s s i f i ed a s strong ac i ds be cause th ey

dis s oci ate virtual ly compl et el y. Thus , we could write the e quati on for the
di sso ciation of HCI in wat er as

Notice tha t we have r emoved the r everse arrow indicating that the re a c tion
' goes t o comple tion'.

I n th e next e xercise, you i l lus t rate the effect on pH of d i lut i on of a strong

ac i d . You us e your a ns wers for compa r i s o n with the di lut i o n e f f ec t for a
wea k acid, which you investi ga t e by ex pe r i me nt .

Exe rc ise 29 Ca l c ul a te t he pH of th e fo l l owi ng a c i d s o l ut io ns fro m

t he g i ve n c onc e nt r a t i ons -
(a) [HCl(a q J] 0 .10 mo l dm- 3
(b) [ HCl( a qJ] 0 .01 0 mol dm- 3
(c) [HCl(aq) ] 0 .0010 mol dm- 3
(d) [ HCl( a q) ] 0 . 00010 mol dm- 3
(Answe rs o n page 93 )

Acids whic h a re not full y di s s ocia t ed in wat er are c l a s sif i ed a s

weak ac ids . I n the f o l lo wi ng ex periment, you inv esti gate how t he
pH of a wea k ac i d varies wi th co nc e nt ra t io n . Befor e you star t t he
tillJ1
expe rimen t , a s k yo ur t eac her to show you how t o use a pH met er; you
need a mete r t o giv e yo u mo r e pre cise value s of pH th an you c an obta in
us i ng pH paper .

23
 EXPERIMENT 1
The pH of a wea k a cid at
various concentra tions

Aim
The purp ose of t hi s e x periment i s t o exa mine
th e ef f ec t of diluti on on the pH o f et ha no ic
ac i d , a weak ac id.

Introduction
Etha noic a cid di sso cia t e s ac c or ding t o t he fol lowi ng eq ua t io n :
CH 3C0 2H( aq) ~ CH3 C02 - ( a q ) + H+ (a q)
The e xte nt of d i ss oc i at i o n dep en ds o n the i ni tial concent ra t i o n of a c i d. By
meas ur i ng the pH at di ffe re nt co ncent rat io ns , yo u ca n see t he effect of
d i lu t i o n . The s e r e sult s can be genera l ised fo r any weak a c i d .

Requ i rem e nts

pH meter wi th gl ass e l ec trod e
wash -bot t le of di s t i l l ed wat e r
a buff er solution (to ca l i b ra t e th e pH met er)
50 c m3 bea ker
0 .10 M, 0.010 M, 0 . 0010 M and 0 .00010 M e t ha noi c a cid s olution s

Proc edure
1. Ca l i br a t e the pH met er by dippin g the g las s electrod e into a s o l ut i o n of
known pH (a buffer solution) and turnin g the adju stin g knob so that th e
scale show s th e correct pH valu e. (If you are in doubt a bout t hi s , ask
yo ur teacher .)
2. Rin se th e g lass e lectrode wit h dist i l led water and di p i t in to a bea ke r
co nta in i ng 0 .00010 M e t ha noic ac id . Reco rd t he pH va l ue i n a copy of
Res ul ts Ta bl e 1 . Return t he el ectrod e t o wate r ; i t must ne ver be dr y .
3. Ri nse t he beak e r with t he next solution , and r e pea t s t e p 2 , working from
the most dil ut e s oluti on to the most co ncentrated .
4. Ente r you r a nswe rs to Exe rci se 29 i n t he se co nd col umn o f Res ults Table 1.

24
Resu lts Table 1

Concent rat io n of Observed pH of sol utions Calcu lat ed pH of sol ution s

ac id mol / dm-3 of etha no ic acid of hydrochl or ic a cid

0 .00010
0 .00 10
0 .010
0 . 10

(Spec ime n r e sult s on pa ge 94 )

Que s t i o ns
1. Compare the p H of e t hanoic ac id with hyd r oc hloric ac id a t each conce n-
trat i on .
( a) I n whi c h of t he t wo ac id s i s t he concent ration of hyd roge n i o ns
grea te r?
(b ) Wha t does th i s te ll yo u ab out th e ex t ent of dis so c iat i on of e t ha noic
ac id compa re d to hydroc hloric a cid?
2. (a ) What happens to t he d i ffe r enc e between the pH of t he t wo a c i d s as
c onc e nt ra tion de cre ases? What does t hi s tell you about the effe ct
o f di l utio n on di s s oc i a t i on ?
(b) Us e Le Chatel ie r 's pr i nc i pl e to e xpla i n t he effect of dil ut ion on
t he e xt en t of disso ciation of ethanoic ac id .
(Answe rs on page 94 )

Si nc e th e pH of a n a cid va r i es with concentra t i on , i f we wan t to

c ompa r e t he st reng ths of dif f er ent ac ids we ne e d to co mpar e pH va l ues
at the s a me c onc e nt r a t i on . You do t hi s fo r you rsel f in th e ne xt
till
JL
Expe r i men t .

P3-B
25
 EXPERIMENT 2
The pH of different acids at
the same concentration

Aim
The purpose of this experiment is to compare
the stre ngths of acids by measuring pH at
the same con centration.
Introduction
You measure the pH of 0.010 M s olutio ns of be nzoic acid, C6H sC0 2 H,
di hydro genphosp hate(V) ion, H2 P0 4 -, boric acid, H3B0 3 , an d et hano i c ac i d ,
CH 3C0 2H. Fro m these measuremen ts you can r an k th e ac i ds in order of strength.

Requirements
pH meter with glass electrode
was h- bo t tl e of distilled wa t e r
a buffer solution ( t o calibrate the pH meter)
bea ke r-, 50 cm3
ethanoic acid solution, 0.010 M CH 3 C02H
ben zoic acid so l ut io n, 0.010 M C6H sC0 2H
boric acid solution, 0.010 M H3B0 3
dihydrogenphosphate(V) ion solution, 0.010 M H2P0 4

Procedure
Measure t he pH of eac h solution, rin sing the electrode f i r s t ea ch time, and
re cord the values in a copy of Results Table 2.

Results Table 2

Concentration
Acid /mol dm- 3 pH

Boric acid 0.010

Be nz o i c acid 0.010
Ethanoic ac id 0.010
Dihydrogenpho sphate(V) ion 0.010

( Specimen results on page 94 )

Question
List these acids in order of de crea sing acid strength.
(Answer on page 94)

26
Yo u should now und erst and tha t th e t erms ' wea k' a nd ' di l ut e' ha ve different
mea ni ng s in c hemi s t r y ; t he same a pplies t o t he te rms ' s t r ong' and ' conc e n-
trated ' . Cons o l i da t e yo ur unders t a nding in the fo l l owi ng Tea cher-mar ked
Exercise .

Teac he r -ma rke d Wri te a sh ort essay comparin g t he te rms : wea k acid ,
Exerc i s e s tro ng ac id , conc e nt r a t e d ac i d a nd dilu te a cid .
Yo u s ho uld s pe nd a bo ut 20 mi nute s on th i s .

In t he ne x t sect ion you ap pl y t o acids wha t yo u ha ve l ea rned abou t equili brium

c onsta n ts i n Uni t P2 .

Dissociation constants of acids

I n Exp er ime nt 1 yo u sa w how pH c ha nges as t he c oncentra t io n c ha ng es ; pH is

ob viously no t a very re l i a bl e meas ure of stre ngt h of an a c i d . The r e i s
ano t he r prope rt y we cou l d us e whi ch i s c ons t a nt a t a ll di l utio ns - t he
e qUi l i br i um c o nsta nt for the d is soc iat ion of a n ac id i n wat e r .

Co ns i de r t he d is so cia t i o n o f eth an oi c a ci d i n wa t e r .
CH 3CO zH(aq) + HzO( I) ~ CH3 C0 2 - ( a q ) + H30+(aq )
The e xp r e s sio n f or the eq ui l i br ium con s t a nt for t hi s reac tion is

[ CH 3 C02 -(aq )] [ H30 +(a q )]

[H 20 ( I ) ] [CH ~ C 02 H ( aq)]
In pr a c t i c e we a l ways omit t he [ Hz O(I)] te r m in a ll e xpress i o ns whi ch refer
to th e di ss oc ia t ion of a n a ci d in wat er . The wat er i s pr e s e nt in such grea t
ex c e s s t ha t it s c oncent ra t ion rema i ns vi r t ua l ly co nst a nt a nd c a n be
combined i n t he ex pres s ion with t he c o ns t a nt , Kc '

If we put th e [Hz O(I)] t erm o n t he o t he r side of t he e xp ress i on a bo ve , i t

becomes :
K [ H 0 CI) ] - [ CH3 COZ -(aq) ] [H 3 0 +(a q ) ]
c 2 - [ CH3C0 2HCaq ) ]
Si nc e co ns t a nt x c o ns t a nt = a not he r co nsta nt , we l e t K x [H 20C I J] = K
c a
We ca l l Ka the ac i d di s s oc iati on c o ns ta nt , whi c h we c a n now e xp r e ss a s :
K - [ CH3 C02-Ca q) ] [ H3 0' Caq J]
a - [CH3 CO z HCa q)]
Thi s ca n a lso be wr i tte n in th e f or m:
[ CH3C0 2 - Caq) ] [ H' Ca q) ]
K
a [CH3C 0 2H Caq J ]

Thi s last e xpr e s sion i s ba sed o n t he. e qua t i on :

CH 3 C0 2HC aq) ~ CH3C0 2 - Ca q J + H'Caq )
i n whi c h t he wate r i s omit ted . This f or m of wr i t i ng the e xpre s si on f o r th e
disso c i a t i o n con s t an t , Ka , of a n ac i d i s t he o ne mo st co mmonly us ed i n te xt-
books and is th e f o rm we have chose n to a dop t i n t his Uni t . So , f o r a

27
general a cid HA dissociatin g in wa ter , we wi l l normal l y write :

Henc e , we will usually write the eq uilibrium law ex pres sion for the disso ci -
ation of an a c i d in the f o r m:

[WC a q J] [ A-Ca q J]
K
a [HACaq) ]
~

Ke va l ues , unli ke pH val ues , a re una f f ec t e d by concentrat ion chang e s and a r e

influenced only by changes in t emperature . So t he value of Ka pr ovi des an
acc ura~e measure of t he ex te nt to whi ch an a cid dis sociates, i .e . the s t r e ngt h
of t hat acid .

The l arge r the value of Ka , then the hi gh er the conc entration of hydrog en i ons
in solut ion and the stronger the aci d . Yo u use this idea in t he ne xt exer~ise ,
in which yo u complete a co py of Ta bl e 2 .

Table 2
,
Acid Equilibriu m in aqueous so l ut i o n Ka /mo l dm- ;:j
Ethanoic acid CH;:jCozHC a q) ? WC aq) + CH;:jCoz -Ca q)
Be nz oic acid C6 HsCo z HCa q ) ~
~ W Caq) + C6H sC o z -C a q )
Carb onic acid HzCo;:j Caq ) ? W Caq ) + HCo;:j - Caq)
Nitrou s acid HNozCaq) ? WC aq) + N0 2 -Caq )
Bo ric ac id H;:j Bo;:jCaq) ? WC aq) + H2Bo;:j - Caq )
Hydro gensulphite ion HSo;:j -Ca q) ? W Caq) + su, 2- Ce q l

Exercise 30 Ca ) Loo k up in yo ur da t a book the va l ue s of t he

dissoc ia t io n c o nst a nts for th e aci ds in Ta b l e 2 .
C b) Use this i nf or ma t i o n t o arran ge th e acid s in orde r
of decrea sing a cid st r en gth .
CAn s wers o n pag e 94 )

We now s how yo u how t o calculate Ka for a weak acid s o l ut i o n fro m pH, a nd the
reverse proces s . For each type of calculation, read th e Wo r ked Example an d
then try th e e xercise s whic h foll ow i t .

Calculating Ka from hydrogen ion concentration (or from pH)

We can use the e xpression for t he dissoc iat i on of an a c i d , HA:
:: [WCaq ) L [ A-Caq) ]
Ka [ HA( aq)]
t o c a lc ulate a va l ue o f Ka for an a cid s olution if we know t he ini t i al
c o nc e nt r a t i o n of t he a c i d and its hyd r og e n i o n c o nc en t rat i o n (or pH) . Yo u
can se e how this i s do ne by wo rk i ng throu gh the fo l low i ng Wor ked Exa mp l e .

28
Worked Example A 0 .100 M so lution of an acid, HA, has a hyd r o ge n
ion c onc e nt r a t i on of 7 . 94 x 10- 6 mol dm- 3 at 25 ° C.
Calculate the dissociat ion constant of this a c i d at .
t hi s temperature .

So l ut i on
1. Write t he equa tion and above i t insert th e init ial concentra tions .
Initial
co nc n/ mo l dm- 3 0. 100 o o

2. Wri te the equilibrium conc entrat ions under the equation . . There must be
the s a me concentration of A- ions produced as hydrogen ions, i .e .
7 . 94 x 10- 6 mo l dm- 3 •
The equilibrium co ncentration of HA = i ni ti a l con centration-
concentra t i on r eacted (0.100 - 7 .9 4 x 10- 6 ) mol dm- 3
I ni tia l
c o nc n/ mo l dm- 3
0.100 o o
HA ( eq ) ~ W( aq) + A-(aq)
Equil i br i um 10-6
(0 .1 00 - 7 .94 x 10 - 6 ) 7 .94 X 7. 94 x 10 - 6
concn/mol dm- 3
Note th a t we have i gnored th e hydr ogen io ns which a r i se from t he ionization
of wa te r . We can do thi s be cause, e ven in pure water, [H +( a q)] is as sma ll
as 1 . 0 x 10- 7 mol dm- 3 , an d t he a ddition of an a cid suppres se s t he
io ni zat i on s till f u r t he r .
3. Wri te th e e xpre ssion for K a f or t his acid and subs titute t h e e qui l i br i um
con cent rati on s:
[W(aqJ] [A-( aq J]
[HA( a q) J (0.100 - 7.94 x 10 6) mol dm 3

6 6
~
But 7 .94 x 10- « 0.100 ( 0 . 100 - 7.94 x 10- ) 0.100
i . e. t he ionization ma ke s v i r t ua l l y no difference t o th e c o nce nt r a t i o n
of HA.

Ka (7 . 94 X 10-6 mol dm- 3 ) Z

-- I
6 3·x 1o-~0 mol dm-- -3- 'I
(0 .100 mol dm 3) L_
·

The followin g two e xerci ses a re si milar : you must deci de f or you r se l f whet he r
yo u ca n ma ke the approxima tion which we ma de in t he Wo rked Example .

Exe rc i se 31 The pH of a 0.010 M carbonic acid solution, HzC0 3 , is ~

4 . 17 at 25 ° C. Calcula t e the value of t he diss oci ation
constant, K at thi s tem perature. ~~\
a
(Answer on page 94 )

Exe r c i se 32 The pH of 5.0 x 10-3 M benzoic acid solution , C6H sCo zH ~

is 3.2 8 at 25°C . Calculate the value of the
disso ciation c ons t a nt at this t empe r a t ur e . ~~

(Answer on page 95 )

The r e are some more questions of this type, for mor e practice or for r e vi s i on
in Appand I x 1C on page 86 .

29
Calculating pH from the dissociation constant
Now we take you through a calculation where you are given a value for the
dissociation constant of an acid and you have to determine its pH at a
particular concentration, i.e. the reverse of our previous e xercise.

Worked Example What is the pH of d 0.100 M solution of ethanoic acid

at 25 °C? (K a = 1.7 x 10-:; mol dm- 3 )
I'of
W
I

Solution
1. Write the equation for the dissociation of ethanoic acid, leaving space
above and below for initial and equilibrium concentrations .
Initial
concn/mol dm- 3

Equilibrium
concn/mol dm- 3
2. Indicate the initial concentrations above the equation.
Initial
concn/mol dm- 3
0.100 o o
CH3C0 2H(aq) ? CH 3C02-(aq) + H+(aq)
3. Let [H+(aq)] = x mol dm- 3
• There must also be the same concentration of
ethanoate ions produced.
And if x mol dm- 3 of ions are pr od uc ed , this must leave (0.100-x) mo l dm- 3
of ethanoic acid undissociated.
4. Now write the equilibrium concentrations under the equation
Initial
0.100 0 0
concn/mol dm- 3
CH 3C0 2H(aq) ~
~ CH3C0 2 - ( aq) + W ( eq )
Equilibrium
0.100 - x x ix
concn/mol dm- 3

5. Write the expression for Ka for this react ion and s ubstitute the equili -
brium concentrations in the expression :
[CH3C0 2-(aq)] [W(aq)]
[CH3C0 2H(aq)]
3
1 7 10 -:; mol d -3 _ (x mol dm- ) 2
. x m - (0.100 - x) mol dm g

6. Decide whether x is small enough to put (0.100 - x) ~ 0 .100

(If this is the case , your calculation is simplified; if not, you must
solve a quadratic equation , as you did in Unit P2.)
Clearly, x is small because Ka is small , but is it small enough to be
ignored relative to 0.100? A simple ' r ul e - of - t humb ' is that if th e
initial acid concentration , c o, divided by Ka , is greater than 1000,
then C o - x ~ c o .

i.e . if Co > 1000 then Co - x ~ Co

Ka

30
 Co _ 0 . 10
7. Her e , ra - 1 . 7 5 588 0 Co - x ~
Co an d you ca n wr i te :
x 10
1.7 X 10 - 5 x2
0 .100
x2 1.7 X 10- 5 X 0 .100
x I( 1 .7 x 10 6 ) = 1.3 X 10-3
[ W ( a q)] = 1 . 3 X 10- 3 mo l dm- 3
8. Sub s t i t ut e this value of [H T(aq)] into the e xpr es s io n which defines pH.
pH = -log [ HT( a q )] = -log ( 1 .3 x 10- 3 ) = - (-3 + 0 .1 14) = ~

(Th e validit y of the s i mp l i f yi ng a ssumption ma de in s t e p 7 can be shown

by solving the quadratic e q ua t i o n at th e e nd of s tep 5 - ~ h i s g ives t he
same answer , but by a tedi ous ro ute.
A simpl er c he c k is to comp are t he c a l c u l a t e d va l ue of x wi th t he init ia l
concentration :
Co - x ( 0 . 100 - 0 .00 13) mol dm - 3 = 0 .0 99 mo l dm- 3
i . e . Co - x ~ Co and t he a s s um pt io n was j u s t i f ied . )

In the follo win g t wo e xerc i s es , yo u mus t jud g e wheth e r or not to make t he

simplifying assumption ma de i n t he Wo r ke d Exa mple .

Exercise 33 ( a) Giv en that t he ionic product of wa t er , [H +] [OH- J,

is 1.00 x 10 - ~ 4 mo1 2 dm- 6 a t 298 K, c a lc ula te t o
t h r e e s ig ni f i c an t fi gures t he pH a t t hi s t e mpe r a -
ture of a 0 .0 50 0 molar aq ueous sol utio n of s odiu m
hy dr o xid e .
(b ) The dissoci ation c o ns t a nt of eth an oic acid at 5 °c is
1 . 69 X 10 - 5 mol d m- 3 • Cal cula t e to t wo si gnif i c a nt figur e s
th e pH of a 0 . 100 molar s o l ut i o n of t his a c i d at 5 °c .
( Ans wer on page 95 )

Exerc is e 34 Ca l c ul ate t he pH of a 0 .1 0 0 M i odic ( V) ac i d sol uti on ,

HI0 3 , at 25 °C .
HI 0 3(aq) ~ HT( a q ) + I 03 - (a q )
( Ka = 0 .1 7 mol dm- 3
)

(Answer on pa ge 95 )

There are some mo r e problems of this type , for more pr ac t ic e or f or revis ion ,
i n Append i x 10 o n page 86 .

In Ex pe r i men t s 1 and 2 , yo u used a solution of constant pH, known as a buffer

s o l ut i o n , to calibrate a pH met e r . Now yo u consi der how a buf f e r sol ution
work s .

31
BUFFER SOLUTIONS (1): CONTROLLING THE pH
In many s ys t ems th e pH is criti cal . The mo st ob viou s e xamples a r e bio lo gical
ones : livin g cells are all ke pt wi t hi n careful l y cont r o l led pH limits,
normall y th e o ptimum pH fo r th e e nzyme ca t a l yze d react io ns tak ing pl a c e
wi t hi n t he m. Ou r bl oo d sta ys r e l ati vel y c ons t a nt at a r ound pH 7 .4 - a c han ge
of le s s than half a pH unit e i t her s ide of th is is e no ug h to t hr ow us i nt o a
co ma. pH co ntrol i s a lso vi ta l ly importa nt in ma ny indu strial pro ces ses, fo r
e xample , in the dyeing and pharma c euti c a l i ~ d ust r i e s .

Sol ut i o ns c ont a i ni ng s ubs ta nc e s wh i ch c o nt r o l t he pH a re known as buffers .

I n this sect i o n yo u te s t a buf f er so lut io n a nd a pply the pri nci ples of
eqUi l i bri um t o exp la i n buff er a cti o n .

Obje ctives . Wh en you have fini s he d thi s section, you s ho ul d be abl e t o :

( 22) de f i ne a buffe r s ol ut i o n in te r ms of
(a ) it s pr opert ies , ( b ) its compos it io n ;
(2 3 ) ap pl y Le Chate lie r 's princ i ple a nd t he equil i br i um l a w t o exp lain t he
ac ti on of a buffer .

As an intro du ction to thi s t op ic , yo u e xami ne th e a c tion of a buffer

so l ut iQn e xpe r ime nta l ly . Yo u compare t he pH cha nges that t a ke pla ce
whe n ac id an d a l ka li ar e add ed t o a buff e r s ol uti on a nd to dis till ed
tID1
water .

EXPE RIM
ENT3
The a ction of a buffer solution

Ai m
The pur pose of the e xp eriment is to c ompa re
the effe cts of adding s ma l l amo unts of a cid
a nd al kali to bu f fe red a nd un b uffered
solution s of t he s ame pH.

Introduction
You are prOVided with a buff er solution des ig ned to maint ai n a pH of 7.0 at
25 ° C and some pure wa t er which , if it i s pur e en ou gh, sh ou ld a ls o hav e a pH
of 7 . 0 at 25 °C.
To samp le s of t he s e t wo li quids . you add s ma l l mea s ured amounts of 0 .1 M
Na OH an d 0 . 1 M HCl, me asuri ng t he pH a t ea c h addi tion.
By comparin g th e pH chang es in th e two s o l ut i o ns you can demon strate t he
action of a buffer sol ution .

32
Requi rements
safety s pectacl e s
2 bu re ttes , 50 cm3 , an d s t a nds
2 funnels , smal l
2 bea ke r s , 100 cm3
hydrochloric a c i d , 0.1 M HCI
sod ium hyd ro xi de s o l ut i o n, 0.1 M Na OH
measu ring cylinder , 25 cm3
bea ker , 50 cm3
- - -- - - - - -- - - - - - - - - - - - - - .- -
-
~
lbt-
..
;~

disti l led water - wa sh -bottl e

buffe r s o l ut i o n, pH 7 . 0 (If no pH me t e r is a vailable us e:
pH mete r full ra nge pH pap er, 1-14
pure water - f r e s h de- i on i z ed water na rrow range pH paper
or freshly-bo iled distil led water th in glass stirring r od )

Procedu r e
1. Fi l l a bure tte with 0 .1 M HCI a nd a nothe r with 0 .1 M Na OH.
2. Usi ng a measu r i ng cyl inder , put 25 cm3 of the buffer solut i on in a
50 cm3 be a ker.
3. Rin se the pH meter e lectrode with dist i l led water from a wash bo tt le ,
and put it i nt o t he bea ker , mak i ng s ure th at t he glass bu lb i s
completely i mme r s ed. Set the me te r t o r ea d 7 .0 .
4. Pl ace t he beak er under the buret te co nta i ni ng NaOH a nd , ma ki ng sure th e
a lka l i does no t fall directly on to th e electrode, add 1 drop of
0 .1 M NaOH . St i r gent l y to e ns ur e t ho r o ugh mi xing and reco r d t he pH i n
a c opy of Resul ts Ta bl e 3 .
If you cannot us e a pH meter , meas ur~ the pH by t r a ns f erri ng 1 dro p of
the mixed sol ut i on o n a glass rod t o a piec e of pH paper . Us e full ran ge
paper f i r st, and t he n narrow range paper t o obtain a more accu rate va lue .
5. Add mor e Na OH to ma ke th e t o t a l vo l ume added 1 .0 cm3 ; measure and record
t he pH as befor e .
6. Add mo r e NaOH t o ma ke the tota l volume a dde d 5 .0 cm3 ; mea s ur e a nd r ec ord
t he pH. Ri nse t he electrode in d i s t illed water and stand it in a f lask of
distil led wate r .
7. Take an othe r 25 cm3 portion of the buffe r , an d measure the pH on the
a ddi tio n of 1 drop, 1 .0 cm3 , and 5 . 0 cm3 of 0 .1 M HC I i n t he same way a s
you di d fo r NaOH . Again , r inse th e e lec trode carefull y a nd sta nd i t i n
dist i l led water .
8. Put 25 cm3 of pure wat er in t he bea ker a nd , keeping it s expos ure t i me t o
the a ir as short as possib le , measu r e i t s pH. If it i s ab so lut e ly pure ,
its pH will be 7 .0 , but i t i s ve r y diffi cult to achieve th is . If the pH
i s l e s s th an 6 . 0 , wash the bea ke r and e lec t rode more ca reful ly an d t ry
aga in .
9. When you hav e a pH between 6 . 0 a nd 7 .0 fo r the ' pur e' wat e r , mea s ure a nd
rec or d t he pH c han ge s on additi on of 0 . 1 M Na OH a nd 0.1 M HCI just a s yo u
d i d f or the buff er· s olution. Take specia l ca r e to wash the e l ec trode when
yo u cha ng e from us i ng al kali to a cid. Record yo ur resul ts in Res ul t s
Ta bl e 3 .
10 . Ta ke anothe r 25 cm3 of pure water , meas ure the pH an d then l eave it t o
s t a nd op en t o t he a ir f or t en mi nute s . Mea s ure t he pH ag a i n a nd r ecord
the res ul t s .

33
Results Table 3

pH on addition of pH on addition of
0 . 1 M NaOH t o 0 . 1 M HCl to
Volume
added buffer pure water b uffer pure water

0
1 drop
1. 0 cm::.!
5 .0 cm::.!

pH of pure water with

mi nim um air exposure

pH of pure water after

10 mins air expos ure

(Specimen resu lts on page 95 )

Quest ions
1. By how much (nearest unit) does the pH of 25 c m::.! pur e water change for
the addition of 1 .0 cm::.! of 0 .1 M HCl?

2. Calc ulate t he ratio :

[ H+ ( a q) ] after add it ion of 1 .0 cm::.! of HCl to pure water
[H +(aq )] in pure water
3. By con t r a s t , the addition of 1 .0 cm::.! 0 .1 M HCl to 2 5 c m::.! of the buff er
so lution s ho uld decrea se t he pH by abo ut 0 .1 , and t hi s corresponds to
i ncreasi ng [H +(aq)] by a factor of only abou t 1 .2 5 . However, the same
number of hydrogen ions were added to both solutio ns . What must have
happened to most of the hydroge n i ons added t o the buffe r?
4. Why does the pH of pure water decrease when e xposed to the a i r?
(Ans we r s on page 96 )

Read ab o ut buffer solutions in yo ur text-b ook (s ) , paying pa rticu lar

attention to Objectives 22 a nd 23 . This will help you wit h the
f ollowing exercises .

Exercise 35 Write a simple de fin ition of a bu ffer solution i n terms

of its properties .
(Answer o n page 96

34
 Composition of buffer solutions

Most buffe r s yst ems co ns ist o f a weak ac id in so l ut io n with its conjugate

base , usual l y t he s od i um or po tassium sa l t of the ac id ,
e .g . etha noic ac id , CH 3C0 2H
so di um et ha noa t e , CH 3C 0 2 -Na +
Howev e r , buf f er s can a l so be ma d e f rom wea k bases i n so l ut i o n with the ir
salt s ,
e .g . ammonia , NH 3
ammonium ch lo r i d e , NH ~ + CI -

This ty pe i s r eall y the same a s the f i r st ; here NH ~ + i s the ac id and NH3

t he con j ug a t e ba se .

To exp la i n how a buffer s ol uti o n is a ble t o a bsorb hyd r og e n i o ns and hyd roxide
ion s f r om a dd ed ac i d and al kali , we c a n us e Le Chat e li e r ' s pr i nc i ple a nd th e
equ i l i br ium l a w.

How acid buffers absorb hydrogen ions and hydroxide ions

I n t he fo l l owi ng Revea l ing Exerc ise , yo u exam i ne the effect of

add i ng hy dro g e n i on s t o a buffe r made f rom 1 . 0 M etha noic ac i d a nd
1 .0 M sod i um e t ha noa te .

01 . Wr i te an eq uat io n f o r t he d i ssoc i at io n of eth a noi c acid .

02 . Look up t he va l ue o f Ka for eth a noic a c i d i n yo ur data book .

03 . From th e Ka va l ue fo r etha noic ac id , do yo u e xpect t hat t he conc en -

trat i on of fr ee hyd rogen i ons i n s o l ut i o n wi l l be :
(a) gr eate r than 1 . 0 mol dm- 3 ,

(b ) a bo ut th e same as t he co nc e nt ra t i on of ethano ic ac i d , i .e .
1 .0 mo l dm- 3 ,
( c) very l ow - mu ch l e s s tha n 1 .0 mol dm- 3 ?

A3 . Very l ow - mu c h l e s s th a n 1 . 0 mo l dm - 3 •

04 . Wha t do yo u ex pect th e conc entrat io n of etha noa te i ons to be?

(a ) Very l ow - about th e s a me a s th e co nce ntra t i on of h yd roge n ions.
(b) About t he same as the co ncen t rat ion of ethanoic acid, 1 .0 mol dm- 3 •

( c) Hi g h - t wi c e the concent ra t io n of e t ha noi c ac i d .

35
A4 . About t he s a me a s th e c o nce nt r a t i o n of e t ha noic ac id .

05 . Expl a i n , wi t h th e he lp of a n e qua t ion , why th e con ce nt rat i on of e t ha noa te

ion i s a s h i gh as thi s .

AS . CH3C0 2 Na(aq ) ~ CH3C0 2 -( aq ) + Na+(a q )

Li ke all s olub l e sa lt s , sodiu m et ha noa te i s c ompl e t el y di ssociated i n
a qu eo us s o l u t i o n s o t ha t a 1 . 0 M s o l ut io n of t he s a l t prod uc e s e t ha noa t e
io ns a t a concentrati on of 1 .0 mol dm- 3 •

06 . What hap pens to th e po s i t i o n of e qui l i b r i um ( i n t he e qua t i o n f ro m A1 )

whe n th e co ncen tra t io n of hyd rog e n i o ns i s i nc r e a s ed by a dd ing ext ra
a cid ?

A6. I t sh ift s to th e l eft, t e ndi ng to r educ e th e con centrat i on of hydrog e n

i on s to wards th e or ig ina l val ue .

Now r ead throu gh a n e xpl a na t i o n of how the s ame buff er s o l ut io n r ea c ts to th e

a ddi t io n of e xt r a hyd r ox i de i on s .

If hyd ro x ide io ns a re add e d to t h e s a me buff e r s o l uti on as us ed in t he

pre vi ou s e xe r c is e , t he y r eact with undi ssocia t e d ac i d mo l e cu l es :
CH3C0 2H( aq ) + OH -( aq) ~ CH3 C02 - ( a q ) + H20 ( 1) ( 1)
The hy d r ox ide i on, be i ng a s t r ong base , r e mov es a pro t on fr om a n e t hano i c
ac i d mo l e c ule , f ormin g wat e r. I n thi s way , fr ee hyd r oxid e ions a r e r emov e d
fr om th e solution a nd t he pH i s not sig ni f ica ntly alte red .

Thi s e xplan a ti on may a ppear different f r om th e one you rea d i n yo ur text-book .

How ev er , the co nven t ional ex pl a na t i o n i s t h e s a me a s the on e we ha ve just
g iven , as a cl o ser l oo k will sh ow.

The e xpla na tio n common ly us e d i s that t he a dde d hyd r oxi de i on s ar e rem ov e d by

combin i ng wi t h hydr ogen i o ns fr om t he se l f - i o nizat i on of wat er :
(2)

Si nce r el a ti vel y few hydrog e n io ns a re ava i labl e i n a weak a cid s o l ut i o n ,

mor e acid i o ni ze s t o i ncre as e t he number of fr e e hyd ro ge n i ons ava i lable :
CH 3C 0 2H (aq) ~ CH3 C02 - (aq ) + "H+(aq) (3)

By ad din g e quat i o ns ( 2 ) a nd ( 3) we get

CH 3 C0 2 H( a q ) + OH- (a q ) ~ CH3C 0 2 - (aq ) + H2 0 ( 1 )
whic h i s t he s a me a s e qua t ion (1 ) .

While th e ac t ua l mec ha ni sm by whi c h thi s r e a c ti on t a ke s pla ce i s not known,

you wi ll app re c ia t e that, si nce un -ioni ze d e tha noic a c i d mol ecul e s a r e mo r e
pl e nt if ul i n solut i o n tha n fre e hydro g e n i o ns, t he fi r st e xpl a na ti on i s mo re
li ke l y .

No w see whet he r yo u ca n a pp l y thes e e xpl a na t i on s to a d i f f er ent buf f er sy st em

by doin g t he nex t e xe r c ise .

36
Exe rc ise 36 Expl ai n how a bu f f er s ol uti o n made f rom pr o pa noi c ac i d , ~
C2 H5 C0 2 H, and sodium propano ate , C2H 5 C02 - Na+ , r esist s
c ha ng es in pH du e t o co ntaminat i o n wit h : ~~

(a) ac i d (b ) a lka li
( Answe rs on page 96 )

To get a mo r e pre c i s e pi ct ur e of the way a buffer r e si sts c hanges i n pH we

can app ly t he equ i l i br i um l aw.

Buffer solutions and the ecu t l ibri um law

Consi der a buff e r made from t he weak a c i d, HA, i n s o l ut i o n wi th it s s odium
s alt , Na+A- . The ac id dissociates in s o l uti o n accord ing to t he eq uat ion :
HA(aq ) ~ H+ (aq ) + A-(aq)

and K = [H +(aq)] [ A-(aq)]

a [ HA( a q) ]
Rear rang ing th is express io n gi ves :

[ W (a ) ] = K [ HA ( a q ) ]
q a [A (aq)]

Since t he "pH of a s o l ution is dete rmi ned by i ts hyd rogen ion conce nt r at ion ,
an d Ka r emai ns co nst a nt, t hi s exp ress i o n s hows t hat the pH of a buff er
solutio n s ho ul d r e main consta nt as long as th e r a t i o of concent r a t io ns of
un -io nized ac id mo l ecul e s to a nion s st a ys c o ns ta nt .

We showed o n page 30 th a t the hydroge n i on co nc e ntra t i on in a 0 .100 M

sol ut ion of e tha noi c acid i s 1 .30 X 10 - 3 mo l dm- 3 • In the Wo rk ed Exampl e
below , we show t ha t , i n a bu ffe r solution made f r om t he s a me a c id , t he
co ncent r at io n of hydroge n i ons present is even l ess.

Wor ked Example Calc ulate th e hydr oge n i o n co ncentra tion in 1 . 0 dm- 3
of buffer so l ut i o n made by dis s o l vi ng 0 .100 mol of
etha noic ac id and 0 .100 mol of sodium etha noate .
K ( CH 3C0 2H) = 1 . 7 X 10- 5 mol dm- 3
a
So l ut i o n
1. Wri t e th e eq ua t ion for the di s s ociati on o f e t hanoic a c id , l ea vin g s pace
a bove and bel ow fo r in itial and eq ui librium amounts . In se r t the ini tial
amounts .
I ni tia l o
0 .100 0 .100
amount/mo l

Equil ib r i um
amount/mol

37
2. Let t he a mo unt o f hyd ro ge n io ns pro du c ed = x mol .
There fore, the a moun t of CH 3C0 2 - at e qui l i br i um ( 0 . 100 + x) mo l and
t he amoun t of CH3C 0 2H at eq uil ib r i um = (0 . 100 - x) .
I nse rt these va lues bel ow t he equa t ion :
Init ial 0
0 .100 0 . 100
amo unt / mo l
CH 3 C02H( eq l .= CH3C0 2 - (aq) + W ( a q)
Equi lib r ium (0 .1 00 + x) x
( 0 . 100 - x)
amou nt/mo l
(You can i gnor e the s ma l l a mount of hy dro ge n ions f r om t he i oni za tio n of
wate r . Their c on cent ra tio n in pure wat er i s o n ly 1 . 0 x 10 - 7 mo l dm- 3 ,
and in th e pre sence of a dded a c id t he io niza ti on i s fu r th er suppre ssed . )
3. Write th e e x press io n f or Ka for ethanoic ac i d :
[ CH3 C0 2- ( a q ) ] [ H+( a q ) ]
Ka =
[CH" C02H(aq) ]
4. Sub st i tute the eq uilibri um c o nc e nt rat io ns in t o t hi s e xpr8s si on . Si nc e t he
volume is 1 .00 dm3 , th e e xp r es sion bec omes :
- 5 = (0 .100 + x) x x
I . 7 x 10 ( 0 . 1 00 - x )

5. The amo unt of hydroge n ions pr oduce d by th e i on i za t i on of e t ha noi c acid

i s norm all y s ma ll . The addi ti on of e t ha noa t e ions su ppr e ss es t he
io ni za t i on still f urther (a c c ordi ng to Le Cha te li er ' s pr i nc ipl e) , so we
can a ssume that x i s s ma l l c o mpa r ed t o 0 .1 00 mol ; thu s we assume t hat :
0 .100 + x "" 0 .1 00 a nd 0 .100 - x "" 0 . 100
0 .100 x x
I::i • The exp ress i o n s impl i f i e s to 1 '. 7 x 10- 5 =
0 .100
x = 1.7 X 10 - 5 a nd [W ( a q )] = 1 1 . 7 x 10- 5 mo l dm- 3 I
In all t he calculatio ns you do whi c h co nce r n buff e r s oluti ons , you c an nBke
s imi lar as sumpt ion s t o t he one s ma de ab ov e . The amoun t s of a dde d wea k ac i d
and salt a r e alwa ys s o much greater t ha n t he a mo unt of hydrogen i o n t ha t t he y
cha nge hardl y at a l l on mi xing . This mean s t ha t you ca n us e the adde d amount s
to c alculate th e equi librium c onc e ntrat ions s i mpl y by div i di ng by t he
tota l vo lu me . A simplifi e d so l utio n t o t he Worked Exa mp l e f o l l ows :

Simpl if ied sol ution

1. Write t he eq ua t io n for the di ssoc i at io n o f e t ha no i c ac id .

2. Write an ex pr e s s io n f o r t he dissocia t io n con s tant , Ka , a nd r ea r r a nge i t

to solve for [H +( aq) ] .

3. Ass ume t ha t t he a dde d a mo unt s of weak a c i d a nd s a lt a re a ls o e quil i br i um

amounts , a nd sub st it ute th em in t he e xpre s si on f or [ H+( aq)] .
3
[ H+( a q ) ] = 1 . 7 x 10 - 5 mo I dm-3 00 .. 100 mo l /1 . o0 dm
100 mo l / 1 . 00 dm3 = 11.7 X 10 - 5 mol dm - 3 I

We sugges t th at you us e t he ful l met hod i n the e xe r c is e whi ch fol l ows, so t ha t

yo u und erstand why you can us e the s i mp l if i e d method i n f utu r e ca lc ula t io ns .

38
Exe r c i se 3 7 ( a) Ca l c ul a te the hy dro ge n io n co nc e nt r at i o n i n a
0 .1 0 M s o l ut i o n of prop an o i c ac i d .
Ka = 1 . 3 x 10 - 5 mol dm- 3
(b) Ca l c ul a te t he hydro ge n io n c on c en t r a t i o n i n a
0 .1 0 M solut i o n of pr o pa noi c a c i d wh ich conta ins
-3
so dium pro pa noat e t o a co nce nt r at i on of 0 . 0 50 mo l dm .
3
As s ume t hat t he t otal vo l um e of t he buff er i s 1 .0 dm •
( c) Compa r e t he hydr og e n i on conc en trat ions tha t you have j us t
c a lc u la ted f or pur e pr op ano i c a cid and pr o pa no i c ac id /
so d i um pro pa noate b uf f er . Use Le Chat eli er 1s pr i nc i ple t o
e xplai n th e di f f e r en c e betwe en t he t wo .
(Answers o n pa ge 96 )

I n e xp l a i ni ng how a buffer sys tem wor ks , we ha v e sa id that th e pH stays

co ns t a nt as long a s t h e r a t io of conc en tra ti on s of a c i d an d c onj uga te base i s
unchan ged . As you ha ve ju st seen , in a bu ff er s o luti o n , t he c on ce nt r a t i o ns
of ac id an d conju gat e ba s e ar e ve ry l ar ge c ompa re d wit h t he co nc e nt r a t i on of
hyd ro g e n ion s . A small cha ng e i n e i t he r of t he se l a r g e qua nt iti es wil l ha ve
v e ry l i t tle ef fect on t he ir r a t i o ; he nce , t he co nc e nt rat i on of hyd r og e n i o ns
i n s o l uti on , a nd t he pH, rema i n a lmo st con s t a nt .

Now t r y a n A-l ev el que s t ion .

Exerc i s e 38 A certain buffer s o lut io n , ma de f rom a weak a c i d , HA ,

a nd i t s s od i um s a lt , has a pH of 5 . 85 . The s o l t i on
wa s ma de by mi xi ng 10 cm3 of 0 .090 M HA an d 20 cm3 of
0 . 1 5 M Na A. Ca l c ul a t e Ka f o r th e a c i d .

( Ans wer o n pa ge 97 )

So fa r in t hi s Un i t , we hav e empha s i sed t he central import an c e of hydr oge n

i o ns in the s t udy of ac i ds a nd ba ses . Howe ve r , i n t he hi s tori ca l de vel opment
of ac i d- ba s e th eori e s , ot he r a spec ts have bee n i mp o rt ant; in th e f inal
s e ctio n of Level One , you co ns i d e r some of t he s e a spe ct s . Yo u may we ll hav e
co ve re d par t of t his work in yo ur pre-A -le vel st ud y , an d it i s mo re i mpor t a nt
fo r so me exa mi na tion sy l lab us e s th an for ot he rs so , be fo r e you s t a r t thi s
s e c ti o n, a s k yo ur te a c her how much ti me you s ho ul d spe nd on i t.

39
HISTORICAL DEVELOPMENT OF ACID-BASE THEORIES
Read about this in at least two text-boo ks which cover the topi c . Q
(As k your t e ac her for g ui dance i f ne cessary - yo u may fi nd t hat fo r ~
this topic , a mor e ' o l d- f a s hi o ne d' tex t wi ll be use f ul . ) The n attem pt ~
the Teacher-marked Exercise which foll ows .

Suitabl e headings for your notes (but not necessarily for an essay) , togeth er
wit h so me sugg estions f or points to ex pa nd , are giv e n b el ow in ch ron o l og ical
orde r .

Early Anon . Sour tast e . Fi nd th e derivat ion of th e wo r d ' a ci d '.

1663 Boy le Definitions of acids an d ba s es i n t erms of te st s ,
indicators , e t c . ( still u s ed in el ementar y work) .
1790s Lavoisi er Acid s co nta i n oxygen . Thi s is not ge nera l ly tru e but
not e a ci dic oxi de s a nd oxoacids.
1838 Liebi g (Also Davy.) Acids contain replaceabl e hydrogen (sti l l
used in e leme nt a ry work) . Find e xc eptions, e .g . NaOH .
1550 s Arrh enius Acid s ~ H+ (aq) . Base s ~ OH -(aq) . Neutrali zation .
Rol e of H20 no t clear. Is anhy drou s HCI an a ci d?
1923 Br0nst ed - As in this Uni t . Show how t hi s theory embra c es Li ebi g ' s
Lowr y and Arrhenius ' th eorie s and a ls o ext e nd s to no n- a queo us
solvents .
192 3 Lewis Not us ually r eq Uired f or A-ieve l (a sk yo ur t ea c her ) .
1939 Usanovich An al l- encompassin g theory (rarely found in text-boo ks !)

The c he mists ' names mentio ne d abov e a r e us eful l abel s but it i s not Vi t a l t o
r emember th em for ex ami na t i on pur po s es . However , some st udents find th e
human interest i n bi og ra phi ca l de tails to be helpful a nd a refreshing c ha nge
f r om f ac t s an d t heori es . There s houl d be s ome bio grap hies a nd histo ries of
chemistry in your school libr ary. Try , f o r insta nce ,
I s a ac Asimov - A History of Chemistry

To co nsolidate yo ur work on the deve lopm ent of aci d - ba s e the or i es , s pend

about 40 mi nutes o n t he follO Wing Tea c her -mar ked Exe r c is e .

Teacher-marked Discuss the ways in which the conc ept s of ' a c i d i t y'
Exercis e a nd ' a l ka l i ni t y' ha ve de ve lop ed since 1777 whe n
Lavoisi er ge ner a l i z ed that all aci ds contained oxygen .
Yo u ma y like to i llustra t e yo ur answe r by re f eren ce to
s ome or all of t he f o l l owi ng s pe cies . but eq ual cr edit
will be given for us i ng e xa~p les of your own choice .
HCI , H2 S0 4 , HS0 4 - , NH3 , H20 , H3 0·, NH4 +

40
 LEVEL ONE CHECKLIST
You have now rea ch ed the end of Lev el One of this Uni t . The followin g i s a
summary of the obj ect i ves in Level One . Read ca r ef ul ly throu gh them a nd
chec k that you have a d equa t e notes .

At this s t ag e yo u s ho uld be a ble to :

(1) & ( 2) e xpl ain why the hyd r ogen ion , H+, i s ver y d iff e re nt from other
pos i t i ve ions ;
( 3) writ e a n e qua ti o n for th e f or ma tion of th e hy dronium i on, H30 +;
(4 ) to ( 6) d efine a n a c id and a bas e in terms of t he Br ¢ ns t ed - Lowry th eory ,
a nd id e ntif y co nj ugate a c i d - ba s e pairs ;
( 7) s (8 ) def ine an amphiprotic substan ce i n terms of a cid -base behaviour ;
(9) to ( 12 ) derive a n ex pre s s i on f o r ~, the i o ni c produ ct of water , a nd us e
i t to cal c ula te [H +(a q ) ] from [o H ( aq) ] and vic e versa ;
( 13) define pH ;
(1 4) & ( 1 5) c a l c ul a t e pH from [H +(aq )] a nd vice vers a ;
( 16 ) c al culate pH from [ oH-( a q)] ;
(17 ) & ( 18 ) di ff erenti at e be twee n strong and wea k ac id s a nd exp la i n t he
effect of di l ut i on o n their pH ;
( 19 ) t o (21 ) wr ite a n e xpre s sion for the ac id diss ociation constan t, K ,
a nd us e i t t o cal cul ate the pH of an a c i d so l ut i o n of k n o ~n
conc en tra t i on ;
(2 2 ) & (23) e xplain what a buffer s ol ut i on i s an d a pply Le Cha t e l i e r ' s
pri nciple and the equil ibrium l a w to e xpl ai n its actio n .

LEVEL ONE TEST

.r.
To fi nd ou t how well you ha ve learn ed the mat e r i a l in Le ve l One , try ? /)
the te s t which follows . Read t he notes be low before s t arti ng .
1. You sho ul d s pe nd about 1 hour on th is t est .
2. Hand your a nswers to yo ur tea ch er for ma rki ng .

41
LEVEL ONE TEST
1. Comp l e te the fo llow ing e quat ion s a nd i de nt i f y the con j uga te acid -ba se
~\~l
pa i rs .
Ca ) HCl( g ) + H2 ° (l ) .=
(b ) + OH-(aq ) ~
~ NH3 (g ) + H2 ° (l )

(c ) HS- Caq ) + .= + H3O +Ca q )

(d) + CN-Caq) .= OH- ( aq ) + HC NCaq) (8)

2. Ex pla in the fa ct t hat th e pH of 0 .1 M hy droch l or ic ac i d i s 1 . 0

bu t tha t of 0 .1 M e t ha no i c a c i d i s 2 . 75 . CNo ca l c ula t io n i s
r eq ui red . ) ~ (4 )

3. (a) Disc us s what you unde r s t a nd by th e t erm ac id . (3)

( b) Def i ne th e te r m pH of a so l ut i o n a nd calcula t e t he pH
val ues of:
Ci ) 5 x 10- 4 M hyd r oc hl ori c a c id ,
(ii) 5 X 10- 4 M so d i um hydro xide s o l ut i o n.
Kw = [H +J [ OH-J = 1 x 10- 1 4 mo1 2 dm- 6 (4)
( c) Defin e t he term a c i di ty c o ns t a nt ( ac id i oniza t i o n c o nsta nt ,
di s s oc i a t i on co ns tan t ) of a n ac id . The ac i di ty co ns ta nt
of et hanoic a c i d (acetic a c id ) at r oom tempera ture i s
1 . 8 x 10 - 5 mo l dm - 3 • Ass um i ng tha t t he e xt e nt of
i o ni za t i on is e xtreme l y small , ca lc ulate the pH of a
0 . 100 M s o l ut ion of e than oic a c id a t tha t t e mp er a t ur e . (5)

4. Comment on t he s tateme nt , I It is the va lue of t he di s s oc i a t i o n

c ons t a nt , Ka , a nd no t pH, whic h pr ovide s a n a c c ur a t e mea s ur e o f
r e l a t i ve a c i d strength . I (3)

5. The pH of 0 .0 4 M me t ha noic acid , HC0 2 H, i s 2 . 59 at 25 ° C.

Cal c ul a t e t he ac id disso cia tio n co ns t a nt a t t hi s t emper at ur e . (5)

6. Expl a i n the act i on of a bu f fe r s o lu t i on bas ed on propano ic

ac id , C2 H5 C02 H. (4 )
Cal c ula te th e p H of a buf f e r so lut i on ma de by a ddi ng 6 . 50 g of
sodi um pro pa noa t e t o 1 . 00 dm3 of 0 .100 M p r opano ic ac id .
K 1 .35 x 10 - 5 mo l dm- 3 at 25 °C
a
[H 1 .0, C = 1 2 . 0, 0 = . 16 , Na = 23 J (4 )

(To tal 40 mar ks)

43
LEVEL TWO

ACID-BASE INDICATORS
An a c id - ba s e indi cator i s a s ubs t a nc e whic h c ha nge s i n c o l our whe n a dd e d to
so l ut io ns of di f f e r en t pH. I t i s, t he r ef o re , us efu l f o r detect ing a c id i t y
a nd a lka l i nit y a nd espe c ial ly f or determinin g when rea c tion s be twe e n a c i d s
a nd bas es a re c ompl e t e .

You ha ve a l rea dy u s ed a nu mb er of ac i d- base indi cat ors , s uc h a s litmus ,

methy l o ra nge an o phe no lph tha le i n . The t erm is often a b br e vi a te d t o th e
s i ng l e wo r d l i nd i c a t or' (as i n many te xt - boo k i nde xe s ) . Mo s t indic ato r s have
two di stinct c ol o ur s , b ut so me ha ve mo r e t ha n t wo .

Ob jec t i ve s . Wh en yo u have f i ni s he d t hi s sect ion, yo u s ho ul d b e abl e t o:

( 24) def in e th e t erm ac id - base ind ica t or ;

( 25 ) e xpl ain wha t i s mea nt by t he pH r ang e of a n a c id -b a s e i nd i c at or .

Rea d t he section in yo ur te xt- book( s ) o n ac id - ba s e indi c a t ors t o

unde r s t a nd wha t th e y a r e and how th e y wor k .

You sho ul d nq w do Expe ri men t 4 , i n which yo u measur e the pH r an ge of

some acid -ba s e i nd i c a t or s .

EXPERIMENT 4
Dete r mi ni ng t he pH r a ng e
of s o me ac i d - ba s e indi c a t o r s

Ai m
Th e purpose of t hi s e xp eriment i s t o s how
tha t d i ff ere nt a c i d- ba se i ndi c a t ors cha nge
c o lo ur o ve r d i f f e re nt r an ge s of pH .

I nt rod uc t i o n
To determine the pH ra nge , you add an a lkal i , 1 . 0 cm3 a t a t im e , t o a
s o l ut i o n c o nta i ning a n i ndi c a t o r an d a buf fe r , a nd measu r e t he pH at ea ch
ad di t io n . The pH va l ue s a t whic h a colou r c ha nge beg i ns a nd e nds d efin e s
th e pH ran ge .
It i s best to mea sure t he pH wit h a pH mete r . Howe v e r , if one i s no t a va i l -
ab l e , you c a n ca lc ula te the pH from a n equat i o n we g ive at the e nd o f t he
e xper ime nt .

45
Requi rements
sa f ety sp ec tac les
3 bure t t es, 50 crrr", and s t a nds }
4 bea kers, 250 cm'l 2 of t hes e may be s ha red
3 fun nels, s mall , for burett es
di st ill ed water
hydroch lori c a cid, 0 .1 M HC I
s od i um hy drox i de so l utio n, 0 . 1 M NaOH - - ---- - --- - ---- --- ---- ---- -
pi pett e, 25 c m'l , and safety f i l l er
buff er so l ut ion , B
3 be ake rs , 100 cm'l
indi ca t o r s ol ut i o ns , in droppi ng bo tt le s , as f ol low s :
l i t mus
met hyl ora ng e
phe no l pht ha l e in
bro moph enol bl ue
met hy l r ed
pH meter ( if a vailabl e)

Proc edure
1. Fill th ree burettes with disti l led wate r , 0 .1 M NaOH , an d 0 .1 M HC I
r e s pect i ve l y.
2. Fro m buret tes , run 25 .0 cm'l of 0 . 1 M HCI a nd 10 .0 cm'l of wate r i nto a
smal l beaker . Simi la r ly , ru n 25 .0 cm'l of 0 .1 M NaOH and 10 .0 cm'l of
wat e r i nt o a s econd smal l bea ker .
3. Pipe t te 25 . 0 cm'l of s o l ut io n B into a third bea ker, a dd 2 drops of an y
one of t he indi cato rs pr ov i ded , an d mix . I f th e co l our i s ve ry pal e,
add a few more dro ps of indica to r, but a lways ad d t he mi nimum a mo unt
which give s a dis tinc t colour .
4. Add the same number of drops of i ndi c a t or to the f i rst two beakers as you
did t o the th i rd . Put these two beake rs a s ide to us e for comparis on
pur poses .
5. Add 0 . 1 M NaO H, 1 .0 cm 3 a t a ti me, t o the t hi r d bea ke r ( co nta in ing B ) a nd
mix the cont ents thoroughly a f te r ea c h a ddit i o n . At th e fir st s ig n of a
colour c ha nge , measure the pH of t he mixtu r e wi th a met er or, i~m e t er
is no t ava ilab l e , r eco r d t he vo lume of a lkal i added . Yo u wi l l be a bl e t o
de tec t a c hange in co lour by compari ng with the beaker conta i ni ng
0 .1 M HC l . Reco r d t he pH , or vo lu me of a lka li added , in a copy of
Res ults Ta bl e 4 .
To ma tch co lo urs pre ci sely , yo u may f ind i t he lpf ul to di lute the
0 .1 M HC I with water so t hat i t has the s ame vo l ume as t he mix ture of
buffer so lut ion a nd NaO H.
6. Co nt i n ue add ing 0 . 1 M Na OH, 1 . 0 cm3 a t a ti me a s before , until t he col our
cha nge a ppea r s to be complete . Comp are the s o l ut i o n with th e b ea ke r
co nt a i ni ng 0 . 1 M NaOH to help you to j udge t he e nd . Bec ord the pH or the
vol ume of a dded a lka l i at thi s point in Results Ta ble 4 .
To ma tch co l ou rs pr eci sely , yo u may fi nd it he lp f Ul to di l ute the
0 .1 M NaOH with wa ter so tha t i t has the s ame vol ume as the mixture of
buffer so lution a nd added NaOH .
7. Repea t s t eps 1 t o 6 f o r a s many othe r i nd icators a s time pe rmi t s . If you
ha ve not meas ure d t he pH va l ue s , ca l cul at e t hem usi ng the e qua t io n under
Results Tab le 4 .

46
Resu l ts Ta ble 4
Co l our change s t a r t s Co lo ur ch an ge en ds
Ind i cat or Initial Final
us ed co lo ur Volume* pH Volu me* pH co lo ur

( Spec imen r es ul t s o n page 97 )

*These c ol um ns need onl y be fil led in i f th e pH ha s no t been measu red . The

pH ca n t hen be c alc ul ated from t he vo l ume, V c m3 , of alka li a dded b y us ing
th e e qua t i o n :
pH 3.0 + 0 .23 V (max V 35 )

Que s t i o n
Why was t he ind i ca to r r ang e meas ured i n a bu ff er so l utio n as o pposed t o a
wate r so l ut i o n ?
(Answe r on page 97 )

The f ollowing t wo 8xe rc is e s ex te nd your knowledge and tes t yo ur under s t andin g

o f pH r a nge s.

Exe rc ise 39 Copy th e out l ine c har t below into your fil e, and us e ~
yo ur expe rimenta l res ults , yo ur dat a book an d/o r
t e xt- boo ks t o compl e t e it . Choose s uitabl e i nd ica tors ~~
s o that their pH range s , shown by bo xes similar to the
e xamples shown, form a s t r a i g ht d iagona l lin e ac ro s s th e
cha rt from bott om left t o t op r i g ht.

indicator pH range

alizarin yellow

litmus red blue

thymol blue red I yellow

o 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Fig.6.

( Ans wer on pa g e 97 )

47
Exercis e 40 ' (a) Look at the cha rt you compl eted in Exe r c ise 39 , ~
and suggest a r ea s o n why li tm us , t he most ·f ami l i a r
indicator in elementar y wor k, is not wid el y us ed ~~
in more advanc ed wor k.
( b) Sug gest another indic ator (i .e . not litmus) whic h c ha nge s
colour aro und t he point where a sol ution has pH = 7 .
(Answer on page 97 )

In the ne xt section , you learn how the colour chang e s of indi cators can be
explained by considering them as weak acids .

Indicators as weak acids

Al l acid-base i ndi ca t o r s ca n be re garded as weak acids and, i n ge ne r a l

disc ussion , a s implified formula , HIn , i s oft en used to r epresent an
i ndi ca t or. In a queo us s o l ut i o n, the i nd i ca t or dissociate s a c co r di ng to the
equation :

Obj ective s . Whe n yo u hav e f i nis he d this se ction, you s ho ul d be a ble to :

( 26 ) explain qualitati vel y how a n a ci d- ba se i ndi c ator wo rks , as s umin g i t
to be a weak a cid ;
( 27) explain how t he pH range of a n a c i d-base indi ca t or is relat ed to
K ' the equi l i br i um constant for its d i s s oc ia t i o n .
I
-n~---.:---------------------

Gen erally , t he two s pe ci e s, Hln and In-, have qu i te dist inct colours , so t hat
colour change s a r e ob s erv ed i f t he eq uil i br i um i s shif t ed to t he le f t , by
addi ng hydrogen io ns , or to the ri ght , by removing hydr oge n i o ns . You have
ob served these colour c hanges i n Exper i ment 4.

Note tha t when a n indi ca tor is used, th e r e i s normall y very litt l e of it

present - f or in stance, two drop s of a di lu t e s ol ut i o n may be a dde d to 25 cm3
of a mixtur e dur i ng a ti tration . This means t ha t t he co ntrib ut io n of t he
indicator it self t o th e t otal hydro gen ion co nce nt r at i on i s neg l ig i bl e . The
to t al hydr oge n ion conc entration i s de termin ed by t he nat ure of th e solution
to whi ch t he i ndica t or i s a dded , an d fi xes t he position of e qUilibrium in
t he system:

co lou r 1 colour 2

Before going f ur t he r in ex pl a i ni ng how a n i nd icat or wor ks , we need to define

two t erms whi ch are commonl y use d in conn e ction with i ndi ca tors .

48
 End-point and equivale~ce point

It is not sur prlslng that ma ny students do not know t he diffe rence betwee n
th e se two terms , beca us e a number of widely - used t e xt - boo ks c onf us e th em or
use t hem in terch angea bly . Only i n spec ia l c i r c ums t a nc e s a re they t he same .

The end -po in t dur ing a n acid -base t it ration is t he stage whe r e t he i ndi ca t or
used ha s a c o l our halfway between i t s extreme colours ; i .e . whe n
[HIn (aq) J
co lo ur A co lo ur B
No te that the end- po int i s a property of the i ndicator a nd do es not
necessa r i l y s how tha t the r e a c t i on between ac id and base is compl ete .

The e qu iva le nce po i nt i s th e s tage r eac hed dur in g an aci d- ba s e t it r a t i on whe n

th e r eact ion be t wee n ac id a nd base is ju st c omplete . The amoun t of ac i d used
i s pr e c i s e l y t ha t r equi r e d by the eq uation t o re act wi t h the amount of ba s e
use d . (Th is is sometimes called t he s t o ic h io me tr i c point . )

Fo r e xample , when 0 .10 M HCl i s ad de d f ro m a burette to 2 5 .0 cm3 of

0 . 10 M Na OH, t he eqUiva lence point is r e a c hed when 2 5 . 0 c m3 alka li ha v e
been a dded . The equation
HC 1 ( a q) + Na OH( aq ) ~ NaCl( aq) + H2 0 (1 )

indi c at es t ha t when equa l a mounts ( 0 . 002 50 mol in t his case) of a c id and

a lka l i hav e been mi xe d , the mi xture cons i sts on ly of sod iu m ch l o r i de solut i o n .
This wi l l have a pH of 7 .0 bec a use Na + i o ns an d Cl - i o ns ha v e no effec t on
hydrog e n i on co ncent r a tion or hydro xid e ion c once ntrat ion .

The end -po i nt may wel l co incid e with t he equi va l en c e point but i t de pe nds on
what i nd i cator i s used ; Exercise 39 sho wed yo u th a t o nl y a f ew indi cat ors
ha ve an end -point a t or ne a r pH 7 . Mo re on t he c ho i ce of i ndi ca t ors follows
t he nex t ex e r cise , which r e i nf orc es t he idea of eq uiv a le nce poin t .

Exerc ise 4 1 What vo lum e of 0 .25 M HC l mus t be added t o 20 cm3 of

0 . 15 M Ba(OH)2 in order to re a c h t he eqUi va lence poi nt?
( An swer on pa ge 97 )

Cho ice of indicator

One of the secret s of succe s sf ul t itra t ion i s to c hoose th e i ndi ca t o r s o t hat

the end-po int coin cides wi t h t he equi va lence point . No te partic ula r ly the
fo l l owi ng poi nt s.
1. The equ i va le nce po int in aci d -base tit ratio ns is no t a lways a t pH = 7 .
2. Only a few acid-base in di ca t or s have a n end -poin t at pH = 7 . Ot hers
c ha nge c o lour at va r io us po i nts over the whole pH sca l e .
3. The e nd- poi nt must be · s ha r p·, i.e . a very s ma l l ad dition of a c i d or
a lka l i near t he eq ui val en c e po int mu st ca use a comp let e c o lo ur c ha nge
in t he indicat or .

49
 The co r rec t cho ice of in di cators de pends o n a simple mat hematical
'r e l a t i o ns hi p whi c h you deri ve i n th e fo l lo win g Rev ea l ing Exe r c i s e .

Q1. Write a g e ne r a l equation for th e di s so ciat ion of a n i nd i cator , Hl n .

A1 . Hln(a qJ <= W (aqJ + I n-(aq J .

Q2 . Wr it e a n e xpre s sio n fo r t he eq ui l ibri um co nstant , KIn '

A2 . K '" [W ( aqJ ] [In-( aqJ ]

In [ Hln ( a q J J

Q3 . Rea r r a nge t he expressio n to so lve for [ H+(aqJ ] .

[Hl n(aq)]
A3 . [W ( aq) J '" K
I n x [I n ( a q)]

Q4 . Take lo ga ri t hm s of the ab ove expression .

Hint: lo g (A x BJ '" log A + l og B

Us e th i s t o se parat e log KI n a nd log [ Hl n ( a q ) J

[ I n ( aq J J

A4 . lo g [H+ ( aq J ] '" lo g K + l og [ Hl n(aq J j

In [In ( a q J ]

QS . Mu l ti ply t he above expression by _1

I .

AS. [Hl n(aq J]

-l og [ W (a q J] "'-l og Kl n - l og [ In ( a qJ]

Q6 . Re pl a c e -lo g [ H+ ( a q ) J by pH a nd -log KI n by pKln ' (It is not on ly in

pH t hat t he pr ef i X p is us ed to mean I- l ogl. )

AB. [ Hl n ( aq J]
pH '" pKl n - log [I n (aq J]

Q7 . Simpl ify A6 to obt ai n a n express io n f or t he pH a t t he e nd -poi nt fo r the

indi cato r .

A7 . The e nd-poin t i s when [Hl n(aqJ J

Then , 10 [ Hln ( aq) ] '" log 1 '" 0

g [In (a qJ]

I:· pH a t th e e nd- po i nt '" pKl n I

50
The e qua ti o n yo u derived i n A6 i s , in fac t , a pa rticu lar case of a mor e ge ne r a l
equat ion
[ac id J
pH = pKa -l og [c onj ugat e base J

which you wi ll fi nd usef ul i n o ther c ontex t s to o , particular l y in calc ulat ions

in volvi ng buff ers . I t i s not eas y to learn th e eq uat ion , but you s ho ul d
certainl y learn t o do the d eri vat ion yo urs e lf .

Now you ca n us e t he e quat io n t o dete rmi ne t he p H ra nge of an indi cator .

Calculating the pH range of an indicator

If we as sume that th e ' a c i d' co l our i s compl etely obscured by the ' ba s e'
col our whe n the concentration of th e base form is t e n-times the c o nc e nt r a t i on
of th e aci d for m; and if we a ssume t ha t the ' ba s e ' co lour i s ob scured by th e
' a c i d ' co lour whe n t he concent ra tio n of t he ac id form is ten -time s t hat of t he
base for m, we can es tab li sh the pH r an g e of a n indi c a t o r .

[HIn (aqJ]
Co l ou r change s ta rt s when [In ( a q ) ] 10 a nd pH pK - l og 10
In
pK - 1
In
[HIn( aqJ]
Co l o ur chang e en ds when a nd pH pK - lo g 1
[ In l eq I] In 10
pK + 1
In
I th e pH ra ng e = ( pK I n - 1) to ( pKI n + 1 ) I

Thus , th e pH r a ng e o f an indi c a tor i s usua l l y two pH unit s , on e ea c h s ide of

pK ' but the a ssump ti on of a ratio of t en t o one i n conc entration s of t he two
I
fo r~s for c ompl et e colo ur maS Kin g i s not a l ways precis ely true . I f you l OOK
at yo ur answe r to Exe r c i s e 39 or you r data bOO K, yo u will s ee tha t pH r a nges
va ry a li t tle f ro m an a verage of two pH un it s .

The ne xt exe rc i s e wi ll show how a Knowl edge of KIn he lp s yo u to c hoos e

s ui t a bl e indi ca t or s fo r t i t r a t i o ns .

Exerc is e 4 2 The e qu ival en ce poin t i n a t i t r ati on be t ween 0 .1 0 M HCl ~

an d 0 . 10 M NH3 occ urs at pH = 5 . Consu lt you r da ta bOOK
(o r Exe r ci s e 39 ) an d ~\\
( a) g i ve one r ea s o n why pheno lphthal ein i s not a suitable
ind i ca t or ,
( b) se le c t an i ndi cat Or you would expec t t o be s ui tab l e .
( An swe r s o n pa g e 98 )

You c a n us ua ll y l OOK up va l ues of KI n in a dat a bOOK b ut t he s e a re , of c ourse ,

expe r i menta l val ue s . I n the nex t s e ct i on we s how yo u how KI n can be mea s ur ed.

51
Measurement of K in values for indicators
Obj ectiv e . Wh en you hav e fi nished t hi s s e c tion , you sho uld be a b l e t o:

( 28) de s crib e a vi sua l me t hod for d eterminin g KIn for an a cid -base indicato r .

You hav e alrea dy see n t hat a knowl e dge of KIn a nd pKIn is neces s ary
in ord er to dec i de whethe r a part ic u l a r in di ca tor is suit abl e f o r a
par ticular purpose. Experiment 4 provided a r ough method f or
measuring KI n, since pKIn i s th e mid-poin t of t he pH ran ge . We g i ve
al t ernativ e methods in Experiment 5 .

EXPERIMENT 5
Determi ning the ion ization
constant f o r a n indi cator

Aim
Th e pu r p o s e o~ this experime n t is t o
det ermin e t he i on i za ti on co ns ta nt ,
KI n ' f or br omophe no l b l ue .

Introduct ion
The re a re tw o met hods yo u ca n use . Bot h mak e use of th e e qua t io n:
[HI n( aq )]
pH = pKI n -lo g [I n ( a q) ]

Yo u prepare t wo s o l ut i o ns : o ne with a hi gh hydr ogen i o n c o nce nt r at i o n i n

which t he ind i ca t or ex ists almo st e nt i re l y as HIn , an d th e ot he r wit h a
hi gh hydroxid e io n c o nce nt ratio n i n whi ch t he i nd ica t or ex is t s al mo s t
e nt ire l y as In - .
Thes e s o l ut io ns are us e d to s how t he c o l our of the indi cAtor at differen t
va l ues of t he r a t io : [HIn(a q)] /[In - ( a q) ]. From t hi s meas ureme nt , yo u c a n
de te r mine t he va l ue of KI n '
Ask your t ea c he r whic h me thod to us e, but it i s a go od id ea to r e ad the
fo l lowing in trod uc tion s f or bo t h method s.

52
Meth od 1 Prepa re two sets of test- t ubes in which the c onc e nt r a t i ons of the
two coloured fo rms of the indicator vary regular ly as shown in Fig . 7 . Yo u
can observe colo urs co rresponding to different va lues of [Hln(aq J]/[In -(aq J]
by looking through two tubes a t once .

increasing [Hln(aq )]
..
CD (3) ® 0 ® ® (j) ® ®
® ® (j) ® ® 0 ® (3) CD
"4
increasing [In~ (aq)]

1
t his pair of t ubes.
vi ew ed fro m the side.
shows the co lo ur when
[Hln(aq )] / [ln - (aq)]= 7/3
Fig.7.

Method 2 Put t wo s olu tions containi ng t he co lou r e d forms in a piece of

appara t us call e d a Bje r rum wedge . When viewed f r om the side , the varyi ng
widths of t he two so lutions give a co nti nuous ra nge of colours . Measu reme nt
of t he widths at any point gives [Hln (aq J]/[ I n- (a qJ ], as in Fig . 8

acidic
7 cm sol uti on
contain ing
alkaline so lut ion Hln on ly
con tai ni ng In - on ly

f
colo ur observed here
correspo nds to
Fig . 8. [Hln(aq))/[ ln- (aq)]= 7/3

Requirements - Method 1 Req uirements - Method 2

safety spectac l es safet y spectacles
measuring cy linde r , 10 c m! 2 bea kers, 250 cm!
20 test-tu bes hydrochloric acid ,
r ac k or rac ks to hold 0 .1 M HC l
2 rows of 9 tubes each measu rin g c yl i nde r , 25 cm!
br omophe no l blue solution bromophenol blue so lution
2 tea t pip ettes Bjer r um wed ge
hydrochloric acid , I ~I stirri ng rod
concen tra te d , HCl - - - - - - - f t sodium hydro xide solution ,
st i r r ing rod 0 . 1 M NaoH
sod i um hydroxide ~ bea ker , 100 ern"
s olution , 4 M NaOH - - - - - - - ~ buffer solution , pH 3 .7
dis t illed water
buffer s ol ution, pH 3 . 7

53
Procedure - Method 1
1. Pour about 5 cm 3 of bromophenol blue solution into a test-tube and add
1 drop of concentrated hydrochloric acid. In this solution, almost all
of the indicator is in the form HIn. Call this solution 'XI.
2. Pour about 5 cm 3 of bromophenol blue solution into a test-tube and add
1 drop of 4 M sodium hydrOXide solution. In this solution, almost all
of the indicator is in the form In-, Call this solution 'Y'.
3. Arrange 18 test-tubes in a rack (or racks) as shown in Fig. 7 and care-
fully add drops of solutions X and Y corresponding to the numbers in
Fig. 7.
4. Add 10 cm3 distilled water to each tube and stir if necessary so that
the colour is even from top to bottom.
5. Pour 10 cm 3 of the buffer solution (pH ~ 3.7) into a test-tube and add
10 drops of bromophenol blue solution. Shake the tube to mix the contents.
6. By holding the buffer tube alongside the pairs of tubes in the rack, find
the pair which is nearest to the same colour.
You will find it helpful to view the tubes against a brightly-lit white
background.
7. Record the value of [HIn(aq)]/[In-(aq)] in the pair of tubes which best
matches the buffer solution.

Procedure - Method 2
1. To 250 cm3 0.1 M HCI in a beaker, add 10 cm 3 of bromophenol blue solution.
Stir well, and then pour the solution into one half of the Bjerrum wedge.
In this solution almost all of the indicator is in the form HIn.
2. To 250 cm3 0.1 M NaOH in a beaker, add 10 cm3 of bromophenol blue solution.
Stir well, and then pour the solution into the other half of the wedge.
In this solution almost all of the indicator is in the form In-.
3, To 25 cm 3 of the buffer solution in a small beaker, add 1.0 cm3 of
bromophenol blue solution. Measure the volume of indicator carefully so
that its concentration is the same in all three beakers. Stir well, and
then pour the solution into the cell which fits on top of the wedge.
4. Slide the cell along the wedge until the colour in the cell is the same
as the colour in t he wedge immediately beneath it, as in Fig. 9.
You will find it helpful to view the wedge against a brightly lit white
background.

cell

. ' . ' ' .

:-: ·. wedg~· .·

Fig.9

5. Record the value of [Hln(aq)]/[In-(aq)] corresponding to the colour match.

This can be obtained by direct measurement, as in Fig. 8. Difficult y in
colour matching may be due to different concentrations; did you measure
the volumes of indicator carefully enough?

54
Calculation - both methods
Substitute your measured value of [Hl n(aq) ]/[In-(aq)] and the given pH of the
buffer in the eq uation:

pH K - l og [HIn(aq) ]
p In [In ( a q ) ]
and obtain a value for pKIn ' Obtain KIn from pKIn in the same way as you
calculated hydrogen ion concentration from pH. Compare your result with the
value given in your data book .
( Specimen results on page 98 )

Que s t i o ns
1. Give two advantages and two di sadvantages of the wedge method compared
with the test -t ube method . You should be able t o answer without having
done both metho ds - look at the introduc tion .
2. Why was as much as 10 drops (Method 1) or 1 cm3 (Method ' 2) of i ndicator
solution added to the buffer solution?
3. Co ul d a bu ffer of pH 8 have be e n used in this experiment?
(Answe r s on page 98 )

The next exerci se test s your knowledg e of indicators .

Exercise 43 The ind icator me thy l red has a pKI n value of 5.1.
Its colours are yellow in acid s o l ut i on and r ed in
alkaline solu tio n. The ionization of this indicator
is represented by :
HIn(a q ) "" W (aq) + In -(aq)
Cal Wha t is the co lour of t he In - ion in solu tion?
(b) On t he a s sumption that when th e concen tration of one
colo ured sp eci es e xceeds the other b y a fa c tor of ten th e
only detectabl e colour is due to th e s pecies in excess,
ca l c ul a t e t he pH range over which meth y l r ed c ha ng es colour .
(c l Calculate the pH of the resu ltin g solution when 1 .0 cm3 of
0.010 M HCI i s added to 499 cm3 of water.
Cdl A few dr ops of me thyl red are added to the s o l ut i o n in (cl .
Cal culat e th e ratio of th e conce ntrat i on of the red form to
that of t he ye l l ow for m in s o lu t i on .
(Answers on pa ge 98 )

The r e are several ' uni ve r s a l' indicators on the market which gi ve a range of
di f f e r e nt colours along the pH s ca l e . The se are a ll mi xtures of simple
i ndica tor s with differ e nt pH ra ng es a nd t he c o l o ur of t he mixture is g i ve n by
' a dding ' the col our s of th e diff erent spe cie s pre s e n t . Care ful c ho i c e of th e
compone nt s can re sult in a series of quit e distin ct colour c ha ng e s , as shown
i n t he next e xercise .

55
Exerc is e 44 Us e you r data book to pred ict the c o l o urs give n a t pH
values 1 , 2 , 4, 6 , Ba nd 11 by a uni vers a l ind i ca t or
contai ning thymo l phthale i n , methyl re d , methyl ye l l ow,
bromo thymol blu e , and thymo l blue .
Assume tha t the in di c a t ors do not r ea c t with each othe r and that
t he amounts of each indicator in the mixtu re are such as to gi ve
col ou rs of equal intens ity . Yo u wil l fi nd it he l pf ul to compl e t e
a copy of Table 4 .
(Th ymol blue ca n e xist i n three d iffe re nt co l o ur ed fo rms and
the refore gives two co lou r changes over diffe rent pH ran ge s . )
(Answe rs on page 98 )

Ta ble 4

Col ou r i n so l utio ns of di ff er en t pH
pH
I ndic ator ra nge pH 1 pH 2 pH 4 pH 6 pH B pH 11

Thymol phtha le in
Methyl r ed
Methyl yellow
Bromothymol blu e
Thymo l blue

' Uni ve r s a l '

Yo u ha ve a l ready us ed di f fe re nt indi ca t or s in some a c i d - ba s e t itrat i ons . In

the next section you learn how to cho ose i ndi ca tor s on the bas is of the way
pH ch a ng es duri ng titrat io ns .

pH CHANGES DURING TITRATIONS

I f an al kal i i s run i nto an a cid in a tit r atio n, th e pH of th e mixtu re sta rts
at a low val ue , depe nd i ng on the s t r en gth and c once nt ra t io n of the ac i d a nd ,
when excess a lkali ha s been added , the pH reaches a high va l ue , dependi ng on
the streng th and concentration of the a l kal i .
In this section o f t he Un it we show that :
(a ) t he chan ge in pH du ring a ti t r at io n i s no t re gul a r ;
( b) the way t he pH changes , as dep icted in pH cu rv es , dete rmi nes t he cho ice
of i ndi ca t or f o r a part i c ula r combi nat i on of a ci d and al ka l i .

Objectives . Whe n yo u have fin ished th is s ect i o n , you s ho ul d be able to :

( 29) sk e t ch th e ge ne ral s hap e of fou r types of pH c urve which show how

pH c hanges duri ng th e cour s e of titra tio ns ;
( 30 ) cho os e su it able a c id - ba se indic ator s for variou s t i t r a ti on s , e xplainin g
yo ur c hoice by refere nce to pH cu rves .

56
The fou r typ es of pH c ur ve
cor r e s po nd t o four t ype s
of ti t ra tio n using a s t rong
or weak ac id and a s t r ong or
STRONG ACID >< STRON~" BsAESE

wea k base . WEAK ACID 4 • WEAK en

Rea d the secti o n of yo ur text-book (s ) dea li ng with pH curves

(so metimes ca l le d t itration c ur ve s ) . Loo k f or the ge neral s ha pes o
of t he f o ur types of curve , a nd note in partic ula r how the pH cha nge s
nea r the equiva lence po i nt .
ITt
You now have th e oppo r t unity to pl ot pH cu rv e s from your ow n
ti trat io n r esult s, in Experiment 6 . Make s ure you obta i n a compl e t e
s et of r e s ul t s, pe rhap s i n cooperat i o n wit h oth er s tudents .

EXPERIMENT 6
Obt a i ning pH c ur ves fo r
acid -a lka l i titra tio ns

Aim
The pur pose of t hi s experiment is to ob tain
c ur ve s which show how th e pH changes du ring an
acid-base titrat io n a nd to us e these c ur ves
t o c hoo s e s ui t ab le indic at or s for di f fe ren t
combina t ion s of ac i d and a lkali .

I nt r od uc t i o n
You have a vail a bl e t wo acids , o ne st ro ng , on e weak . and t wo alkal is , one
s trong , on e weak , gi vi ng f o ur possib le c ombinations . Yo u shou ld st udy th e
r e s ult s of ea c h of th e f o ur combina t i ons eve n i f yo u cannot complet e f our
yourse l f .
For eac h co mbi nat i on , yo u run the a l ka l i fro m a b uret te , in smal l s t e ps, i nto
25 cm ~ o f t he ac id a nd measure the pH at eac h addit ion . You then pl ot pH
ag a i ns t vo l ume of al ka l i added . I t i s bes t to measure pH with a pH meter ,
bu t it i s pos s i bl e t o get adeq uate res ul ts us i ng na rrow-range pH pa~ e r i f a
mete r is no t a vail abl e. Us i ng a magne t ic s t irre r speeds up the e xpe r i ment
but it is not e s sen t ial.

P3-C
57
Re qu i rements
sa fe ty spectac le s
pH met er or na r row r an ge pH pa pe r s to cove r pH 1 to 14
et ha noic a cid , 0 .100 M CH ~ C 0 2 H
pipett e , 25 cm3 , an d sa fe ty fi l l er
be a ke r , 100 c m3 or con ical f las k, 2 50 cm3 a nd th in g la s s ro d
magn etic st irr er ( if a va i labl e )
2 buret t es , 50 cm3 , an d s t and s
2 f unne l s , sma l l , for fi l l i ng bure tte s
4 bea kers , 250 c m3 , wi th l a bels
ammon ia solut io n , .0 . 100 M NH 3
dis t illed wate r
hydro chlori c ac i d , 0 . 100 M HC I -=='
s od i um hyd r o xi de solut i on , 0 .100 M NaO H

Pro c edure
-~
II> . ill

1. Pi pet t e 25 . 0 cm3 of 0 .1 00 M et han oi c ac i d into a 100 cm ~ be a ker , a dd a

s ma ll s t irring pad dl e , a nd s ta nd th e be ake r on a ma gne t ic sti rr e r .
2. Ca re f ul l y c l a mp t he e l e c t r ode of a pH me t er s o t ha t t he bu lb i s complete ly
i mmers ed in t he ac id a nd i s c l ea r of the s tir ri ng paddl e . If a magn et i c
st irre r ( o r mechan ical st i r re r) i s not ava i lab le , you will have to s wi r l
t he bea ke r by ha nd . If a pH mete r i s not a vai lab le , it i s be t t e r to use
a c o nica l fl a s k r athe r tha n a bea ker .
3. Fil l a b ur et t e wit h 0 .1 00 M a mmoni a s o l ut io n and c lamp i t ove r t he b ea ke r
(or fl a sk) c o nt a i nin g th e a cid .
4. Ob ta in a va l ue of t he pH of t he ac i d , e ith e r by r ea din g th e pH meter
( whi c h mus t , of co urse , ha ve been ca l ib ra ted ) or by r emo vin g 1 s ma l l drop
o n a t hin g la s s r od a nd tes t i ng wi th nar row r a ng e in di ca to r pape r . If
you do not know whic h r a nge to use , test fi rst wit h f ul l r an ge Uni ver s al
in di ca t or paper . How eve r , it is i mporta nt not t o remove more tha n t he
min im um a cid fro m the f l as k .
5. Add t he a l kal i fro m th e bu r et t e i n s t eps as sho wn i n Re s ult s Ta ble 5
a nd r ec o r d t he pH a t e a ch a ddi t io n af t er th oroug h mix in g .
(T he volumes shown in th e t a bl e s were c hose n on t he a ss umpt ion that the
ac i ds an d al ka l i s ha ve pre c is e l y t he s a me c once nt ra t i o n, so t hat th e
eq uiv a le nce poi nt i s a t 25 . 0 cms ad ded a lkal i . I f t hi s i s no t t he ca s e ,
t h e volumes wi l l ha ve t o be a dj us ted s omewhat . As k yo ur t ea c her ' s ad vi ce
on th is . )
6. Repea t s t e ps 1-5 wi th a t l ea s t one o the r c omb i na t i on of a c id a nd a lka l i ,
a nd co mpl et e a copy of Res u l t s Ta b l e 5 . If you do no t ha v e ti me to do all
t he e xp eri ments , yo u ca n s ha re da t a wit h oth e r s tude nts , or us e o ur
s pec i men re su lt s .
7. Pl ot f our c ur ve s , on on e sheet of gra ph paper . The usual convent i on i s
t o s how t he pH on the vert i ca l s ca le , and t he vo l ume of a dd ed al kal i o n
t he ho r i zont a l s ca le .

58
Res ults Ta bl e 5

0 . 100 M NH3 a dd ed t o 25 .0 cm3 of 0 . 100 M CH 3 C02 H

Vo lu me/cm 3 0 .0 5 .0 10 . 0 15 . 0 20 .0 24 .0 24 . 2 24 .4 24 .6 24 .8 24 .9
pH
Vol um e/ cm3 24 .9 5 25 . 0 25 .05 25 . 1 25 .2 25 . 4 25 .6 25 .8 26 .0 30 .0 35 .0
pH

0 .1 00 M Nao H ad ded t o 25 .0 cm 3 of 0 .100 M CH 3C0 2 H

Vo l ume/c m3 0 .0 5 .0 10 . 0 15 . 0 20 .0 24 . 0 24 . 2 24 . 4 24 .6 24 .8 24 .9
pH
Vo l ume/cm3 24 .95 25 . 0 25 . 0 5 25 . 1 25 .2 25 .4 25 . 6 25 .8 26 .0 30 . 0 35 . 0
pH

0 . 100 M NH3 a dde d t o 25 .0 ern" of 0 .100 M HCl

Vol ume/c m3 0 .0 5 .0 10 .0 15 .0 20 .0 24 .0 24 . 2 24 .4 24 .6 24 . 8 24 .9
pH
Volume/cm 3 24 .95 25 . 0 25 .05 25 . 1 25 . 2 25 .4 25 .6 25 .8 26 . 0 30 .0 35 . 0
pH

0 .1 00 M NaoH added t o 25 .0 cm3 of 0 . 100 M HCl

Vo lu me/ c m3 0 .0 5 .0 10 .0 15 .0 20 .0 24 . 0 24 .2 24 . 4 24 .6 24 .8 24 .9
pH
Vo l ume/c m3 24 .95 25 . 0 25 . 0 5 25 . 1 25 . 2 25 .4 25 .6 25 .8 26 .0 30 . 0 35 . 0
pH

(S pecimen res ul t s o n pa g e 99 )

Ques t io ns (Answe r fo r ea ch pH curve)

1. Ove r wha t sec t ion of t he c urve ( i f any) d id t he pH c hange by 2 un i ts f or
th e addit io n of 0 .2 cm3 (o r l e ss ) of a lkal i ? Answer in t he fo rm of
I pH Y to pH z I •

2. At what vo l ume of alkal i was t he e qu i val e nce poi nt ?

3. By how much (app r ox imat ely ) woul d the pH c hange on t he add i t ion o f o ne
extra drop of a lkal i (0 .05 cm3 ) a t 12 .5 cm3 , 25 .0 cm3 , 34 .0 cm 3 of a dd ed
a lka li ?
4. What indi cator (s) (if any ) wou ld be s ui tab le fo r this titra tion? To be
s ui ta ble , the indi ca t or mus t hav e a n en d-point whic h coincid e s with t he
eq uiva l e nce poi nt , an d t he en d-p oint must be ' s ha r p' , i .e . the col our
change must be complete fo r a ve ry sma ll add it io n of a lka l i - prefe r ab ly
on e dro p (0 .05 cm3 ) .
(Answe rs o n page 99 )

The ne xt exerci se tests your unde r s t a ndi ng of pH c ur ve s .

59
Exercise 45 A few d rops of pheno lphthalein ind icator are add ed to
26 c m3 of 0 .1 0 M so dium carbonat e so lu tion a nd the
mixt ure is t itr ated with 0 . 20 M hydro chlo ric a ci d un ti l
i t beco mes co lourless . Some methyl ora nge i s now added
a nd t he t itratio n i s cont in ued until the s ol ution aga in c ha nge s
colo ur . The diagram s hows how th e pH chang es dur i ng the
titration and a l so show s the pH range of some indi cators.

o 5 15 20 25
volume of Hel added / cm 3

Fig. 10.

(a) Wr i t e down tile ti tres ( titrat io n volumes) corresponding to

t he two co lour changes .
(b) Wri te an e qua t i on for th e reaction between hydrogen ions
a nd carbonate ions whos e e nd- po i nt is indicat ed by
phe no lphthalein . This re action ta kes pl a ce without
evolution of gas .
(c ) Which of the two e nd-po ints i s the sharper? Give th e
ev i de nce on which your an swer is ba se d .
( d) (l I For the i nd i ca t or phenolp hthalein , write down the
value of pK a .
( ii ) What is th e va lu e of Ka'7
( e) What would yo u ob serve i f yo u a t tem pted to tit r a t e 2 5 cm3
of 0.1 0 M sod iu m carbonate so l ut ion with 0 .20 M hyd r oc hl or i c
a cid using bromot hymo l blue as ind icator? ( Bromothymo l b l ue
is ye llow i n a cid ic solut i o n , bl ue i n al kaline sol ut ion . )
(Answers on page 99 )

pH curves ca n be draw n fro m ca l c u l a t e d va lues of pH, as we s how i n t he ne xt

sect i on .

60
 pH curves by calculation

It is ~ossible to c a l c u l a t e ac curate ly t h e p H at an y po int du r i ng a ti tra tion

f r o m a kno wl edge o f t he d i s s o cia tion co nsta nt s f o r t he ac i d a nd a lka li , an d
th e i r c o n c e nt r a tion s . We sh ow yo u o n l y the simpl e st type of c a l c u l at io n h er e
b e caus e it i s f r e q u e nt l y i nc lu d e d in examinatio n pa p e r s ; this is th e
calc u l a t i o n o f p H fo r s t r o n g ac id- s t rong base ti tra ti o n s .

Yo u c a n calcu late th e pH at any s tage d ur i ng t he ti tra ti on by ca lc u l at i ng t h e

amo un t o f e xcess a cid b efore t he eq ui va le nce po i nt , or the amo unt o f ex c ess
a lka l i a ft er t he eq ui vale nc e poi nt . Fro m th i s a mount yo u ca n c alc u lat e t he
pH a s previo usl y d e s c r ib ed .

Worked Exampl e Ca lc u l at e t he pH of th e s ol ut i on r e su l t ing from

addin g 7 .00 c m3 0 .100 M NaoH to 25 .0 cm 3 of
0 .100 M HCI .

So l ut i o n

Amo u nt of acid i ni ti a l l y = cV = 0 .100 mol dm- 3

x 0 .0250 dm3 = 2 . 50 x 10- 3 mo l
Amount o f alkali add ed = cV 0 . 100 mol d m- 3
x 0 .0 07 0 0 dm 3
= 7 . 00 x 10- 4 mol
Ac co rd in g to th e e qu a tio n :
Na o H(aq) + HCI ( aq) ~ NaCl( aq) + H2 o ( 1 )
t he amo un t of a c i d r ea c tin g = t he a mo un t o f al ka l i adde d .
The a moun t of a c i d left i ni tial amoun t - amo u n t react e d
( 2 .5 0 X 10- 3
- 7 .00 x 1o- 4)m ol 1 .8 0 X 10 - 3 mol
To t a l vol ume o f solution = 2 5 .0 cm 3
+ 7 .0 cm 3
32 .0 cm 3

[ H+( a q ) J· = [HC l(aq)J· = n/V = 0 .00180 mol 0 .0 56 3 mol d m- 3

0 .03 20 dm3
pH = - log [H +(a q)J = - ( - 2 + 0 .75 1) = +2 - 0 .75 = ~

Wo r k e d Ex a mpl e Calcula te th e pH o f the solution r e s u l t i ng f rom

addi ng 2 5 . 2 c m3 of 0 . 100 M NaoH t o 2 5 .0 c m3 of
0 .0 500 M H2 S0 4 ,

So l u t i o n
Amo u nt o f ac id i n i t i a l l y = cV = 0 . 0 500 mo l dm- 3
x 0 .02 50 dm3 = 1 . 25 X 10 - 3 mo l
Amount o f a l ka li a d d e d = cV = 0 .100 mol dm- 3 x 0 .0252 d m3 = 2 .52 x 10 - 3 mol
Ac c o r d i ng t o t he ba lanc ed equa tion :
H2S0 4( aq) + 2 Na oH ( a q ) ~ Na 2S o 4( a q ) + 2H 2 o(1 )
th e amo un t of a lkali react i ng tw i c e t h e ini t ia l amo unt of acid .
Th e a mo u nt o f excess' alk al i amou n t a dd e d - amount r e a c t e d
2 . 52 X 10 - 3 mol - ( 2 x 1 . 2 5 x 10- 3 ) mo l
5
2.0 x 10 - mol
To t a l vo lume of s ol ut ion 2 5 . 0 c m3 + 25 .2 c m3

61
Sol ution (cont . J
5
:. [OH-(aq) j = [ Na OH(aq J j = n/V 2 .00 x 10- mol = 3 9B X 10- 4 mol dm- 3
0 . 0 50 2 dm 3 •

But K = 1 .0 0 X 10- 1 4 mo 1 2 dm- 6

w
K 1 .00 X 10 - 1 4 12 d - 6
[ H+(. aq Jj w mo m = 2 .51 x 10 - 11 mol dm- 3
[ OH ( aq l ] 3 . 9 B x 10 4 mol dm :3
pH = - l o g [W(aq) ] = - ( - 11 + 0. 40 0 ) = +11 -0.400 = ~
Note that a differe nce of only 0 .2 cm:3 of alkali be t we en t his po int a nd the
equivalence poi nt at 25 .0 cm3 gives a large difference in pH , 7 .0 ~ 10. 6.

Use a met hod similar to t hat in the Worked Examples to do the next exerc ise .

Exe rc ise 46 25 .0 cm3 o f 0 . 100 M Hel was t it rated with 0 .100 M NaOH .
(a ) Calcu lat e the pH of th e s o l ut i o n for each of the
foll owing volumes of NaoH :
0 .0 , 5 .0, 10 .0 , 2 0 .0 , 24. 0, 2 5 .0 , 2 6 . 0 and 30 . 0 cm3
(b ) Plot a ti tration curve ; i. e. pH ( ve r tic a l axis) agains t
vol ume of NaOH added (horizon ta l axis) .
(c) What i s a s uitable in d i c a t or for t hi s ti t r a ti on ?
(Answers on page 100 J

I n Exe r c i s e 4 6, you ma y ha ve fou nd it a lit t le te diou s to do seven s imil ar

calculations . Neve rthe less , you should have real ised tha t seven calcu la tions
wer e i ns ufficient to give a good pH curve - t here were s o me s e r i o us gaps ,
especially i n the r egion where the pH was cha ng i ng most rapidly . You c a n ,
of course , fi l l i n these gaps for yourse lf by doi ng ex tra calc ula t ions ;
alt ernat ively , yo u can le t a computer do the work , i f a s ui table program i s
available .

pH curves by computer

The re is a n ILPAC comp ut er prog ram c a l l ed ' pH c urves ' wh ic h does a l l ~

t he ca lcu lation s ne c e s s a r y for plo tt ing pH curv e s and displ ays t he
curves on the s c re e n in high resolution graph ics . The program not
only de a l s wi t h the strong a c i d - s t r o ng ba s e comb i na t io n but a lso
plots c ur ve s for t itrations in vo l vi ng wea k a c i ds and bases where t he
ca lc ulations are a l ittle more diff ic ul t . In a dd i t i o n , you c a n use the
prog ram to chec k on the suita bility of acid -base indi cat or s.

Yo u do not n e e d t o know anything about comp uti ng but , i f yo u have not us e d a

pr o gr a m be fore , you will ne e d a few min utes i nstr uct io n on gett ing started
a nd using t he ke yboa r d . Ask yo ur t ea c he r f or the s tuden ts ' notes accompany i ng
th e pro gra m, and s tud y the m befo re yo u si t down at th e compu ter .

Yo u ha v e real is ed by now t ha t t h e mixture a t t he equ ivale nce poin t o f a

ti tra tio n betw een a n acid an d a n a lkal i does no t a lways ha v e pH = 7. We
consid e r th e reasons for this in the ne xt s ectio n o n hyd rolys is of sa lts .

62
HYDROLYSIS OF SALTS
At th e e qui val ence point th e r eac t i on be twee n a c i d a nd base is compl et e , so
t ha t only a s o l ut ion of t he sa lt r ema i ns . I f th e sal t i s de r iv ed f rom a
s t r ong ac i d an d st r o ng ba se , e .g .
HC1( a q) + NaOH( aq) ~ NaCl(a q ) + H20 ( 1 )
t he n t he i on s pr e s e nt , i n t hi s ca s e Na + a nd [ 1- , show no t e nd en c y to r ea ct
wi t h water t o c ha ng e t he pH fr om t he va l ue of 7 f or pu re wat er , i . e . fo r
NaC l(aq ) , pH = 7 .

How ev e r , a s al t deri ved fro m a weak a cid , e. g . e t ha no i c ac i d , c ha nges t he pH

bec a us e th e i o ns rea c t with wat e r t o give a n e xce s s of hy drox i de i on a nd a
pH great e r t ha n 7;

Si mi l a r ly , a sa l t deri ved from a wea k ba se , s uc h a s a rrrro rri a , cha nge s th e pH

bec a us e th e i on s reac t wi t h wate r to g ive a n e xc ess of hydrogen i on s , and a
pH le s s t ha n 7 ;

Thes e r ea c tio ns are exa mpl e s of wha t i s r efe r red t o i n ma ny text s a s

Ihydrol ysi s of sa lts ' .

Obj ect i ve . Whe n yo u ha ve f inis hed th is se c t i o n, yo u sh oul d b e a ble t o :

( 31 ) des c r i be how a s al t a ff ec ts the pH of it s solut io n .

Look in t he i nde x of yo ur tex t -boo k und er Ihydr o l ys i s' and read th e

se ctio n dea l i ng wit h s a l t s . Thi s wil l he lp you wi t h the ne xt e xercise o
a nd the ca l c ul a t io ns ( i f yo u a tt e mp t t he m) . ill
Exerc i s e 47 Wh en each of t he fol low i ng sal t s i s d i s sol ved in wat e r
i s t he pH grea te r t han , le ss t ha n , or equa l t o 7 ?
Writ e equ at ion s to sh ow t he r eac ti on wi t h wa ter , i . e .
hydr ol ysi s .

(a) Pot a s s i um cya ni de , K+CN-

(b) Sod i um ca rbo na t e , ( Na +) 2C0 3Z-
(c ) Sod iu m fl uo ri de , Na +F-
(d ) Ammon i um su l ph at e , (NH4+ ) 2S0 42-
(Answe r s on pag e 10 0 )

As k yo ur teac her whether your syllabUS r eq ui r e s yo u to be ab l e to ca lc ul at e

the pH of sa l t solut ions . I f s o , t urn t o Appendi X 2 on pa ge 89 .

We now t a ke a se co nd , more de t ai l e d , l oo k a t buff er s ol utions .

63
 BUFFER SOLUTIONS (2)
Fro m Level One , you al r ea dy know somet hi ng a bout t he a c ti on of b uf f er
s ol ut i ons . We now giv e a mo r e de t ai l ed exp l a nat i on of ho w t he y wor k, us i ng
t he equ i li br i um. l a w a nd a n ex pe r ime nt in whi c h you make a nd tes t the a c t i on
of a buf f e r s ol ut i on .

Obj ec tive . Wh e n yo u have f i ni s hed t hi s se c t i on , yo u s ho uld be a bl e t o :

( 32) e xpl a i n why th ere i s a sma l l c han ge in pH f o r relat ive l y l arge

a dd it ion s of a lkal i in ce r t ai n r e gi o ns o n a ti tra ti on c ur ve .

Rea d a ga i n the se ction o n bu f f er s i n yo ur t ext - boo k, pay i ng pa r t i -

CUlar a t t e nt i o n t o th e mor e ma t hemati ca l pa r t . Thi s wi l l be und er o
s ub - hea di ngs s uc h a s ' ca l c ul a t i ng th e pH of bu ff e r SOl ut io ns ' .
Ref e r back to yo ur text -book as ne c e s s a r y while you work t hr oug h th e ill
ex e r c i se s .

We be g in t hi s s ec t i o n by lo ok i ng a ga i n at so me pH c urves .

Buffering regions of titration curves

Yo u pl ot t e d t i t r a t i on curv es fo r s t r o ng a nd weak a cid s a nd ba s es . Your c ur ve
f or th e t i tr a tion of e t ha no ic a cid with so di um hydr ox i de ha s t his sh a pe :

.1. j .. 1_.

. : L~" :~ ~1~ :~~+~~ ~'-- -,-~j . .~~f~' --

i : ",:::J:::: :::j:.: i ii
o 5 5 20 25 30 35 40 45 50
volume of alkali added/ern -
Fig.11.

64
Not ice t hat th e c u rve f la tt ens ou t in t he r egio n befo re ne ut r al i za t i o n, i . e .
th e re i s a very s ma l l c han ge i n pH f or th e ad d i t i on of a l a r ge amo unt of
a lka l i . At t hi s po i nt i n t he tit rat i o n , s ome e t ha no i c a c i d mo l e cul e s hav e
bee n neutra li z ed b y hyd r oxi de i o ns f r om the a lka l i :
CH 3C0 2 H(aq ) + OH-(aq ) ~ CH 3C0 2 -(aq ) + H2 0( I )

Although hyd rox ide ion s ar e co nt i nua l ly be ing ad ded , t he change i n pH i s

sl owed down by buff e r ing act io n . As t he abo ve equa t io n s hows , t he a mo unt of
a cid a nion increa s es a s hydro xide ion i s added . Wh e n the co nc ent ra t ion of
anio n r ea c he s a bou t t he same l e v e l a s t he co nce nt ra t ion of un - io nized a c i d ,
a nd bot h ar e mu c h greate r t han t he c o nce ntra t i o n of f re e hydro ge n i o n, t he
s o l ut i on is a bu ff er .

The a c id di s socia ti o n co ns ta nt i s give n by the e xpr e s s io n :

[ W (a q)j [ CH3 CO z - ( a q) ]
[ CH3 COz H( aq J]

[ W (a q )j

Sma l l cha nges in the conc en trat ion of e it he r un - i o ni z ed acid or it s co n j ugate

ba se ha v e very l i t t l e effec t on th e con c entra tion of hydro gen ions so t hat
th e pH re ma ins re lat i vel y c onstant .

I n t he nex t e xercis e , you c a l cu l a t e t he pH a t t he mi ddl e of the bufferi ng

r egi on when ethano ic a cid i s t it rat e d wi t h s odi um hydro xide .

Exe rcis e 48 25 . 0 c m3 o f a s o l ut i o n of 0 . 10 M e thanoic aci d i s

tit ra te d with 0 . 10 M s od ium hyd r o xi de. When suffi c ie nt
s od ium hydro xi d e ha s bee n ad ded to neu t r ali ze ha lf the
etha no ic acid ( the 'hal f ne utra liza t i on poi nt ' ) , ca lc ula te :
(a ) t he co ncentrat io ns o f et ha no ic ac id and ethanoa te i o ns,
( b) t he pH of t he solu t ion .
Ka ( CH3C OzH) 1 .7 x 10 - 5 mol dm- 3
( Answe r s on pa ge 100

E x~ r c i s e 49 Loo k ba c k at yo ur own t i tration c ur ve fo r e tha no i c a c id

a ga i nst sodi um hydrox i de . What i s th e pH a t t he centre
of th e ' f l a t t e ne d r eg i on ' before ne utra l iza t i on? Does
4
~~\ \_
yo ur r e su lt agr ee wi t h t he va l ue yo u hav e jus t c a l c u-
l a t ed in Exercise 48?
(Answe r on page 100 )

65
pH of a buff er sol ution

Objective . When you have finishe d this s e c t i o n , you s ho u l d b e ab le to :

(33) calculate t he pH of a buffer solution .

As yo u hav e jus t found i n Exerci se 48 , it i s a fa irly s i mp l e ex e r c i se t o

ca lculate th e pH of a buffer s o l ut i o n , knowing K a for the weak a cid and t he
co nce ntrations o f weak acid and c o njugate bas e i n so lu tion . To make sure you
are conf ide nt about this type of cal c ulatio n , do t he next two ex ercises .

Exercise 50 Calculate the pH of a s o l ut io n which co nt a i n s

0 .10 mol dm- 3 of pro pa nOic a c i d a nd 0 .050 mo l dm- 3 of
sod ium propanoate .
Ka ( CH3 CH2 C0 2 H) = 1 .3 x 10 - 5 mol dm- 3
( Answe r 0 n page 10 0 )

,
Exerc ise 51 Calculate t he pH of the followi ng bu ffer solu tions
contai ning buta no i c acid and po tassium but a noa t e.
[ CH 3CH2CH~C02HJ/mol dm- 3 [CH3C H2CH2 C02 -K +]/mol dm- 3
(a ) 1 .0 1. 0
(b) 2 .0 1 .0
( c) 2.0 0.5
(d) 0 .5 2 .0
(An s wer s o n page 101 )

For ex tra practice i n this type of proble m, see Appe nd i x 1E o n page 87 .

Now we co nsid er th e smal l changes in pH which occur when a buffer solutio n

is co ntami nated .

Contamination of buffer solutions

In Le vel One , yo u f oun d that th e pH of a buffer s ol ution s t a y s a l mo s t consta nt ,

even i f fairly l ar g e amo unts of ac i d or a lkal i a re add ed to it . In t hi s
sectio n , yo u lear n how t o c al c ula te t he c hang e i n pH tha t would b e expect e d
whe n a buffe r i s c o nt a minat ed wi th e i the r ac id o r a lkal i .

Objec t i ve . Whe n yo u ha ve f inished thi s sect io n , yo u s ho ul d be able t o :

( 34) ca lc ula te the ch ange i n pH t hat t a ke s p lace when a b uff e r is co ntami -

na te d by th e a dd i t ion of ac i d o r alka l i .

Rea d t hrou g h t he Wo r ked Examp l e and t hen do t he ex er c ises whi ch follo w.

66
Worked Exa mpl e A 1 . 00 dm~ bu ffe r solu t io n con t a i ns 0 . 500 mo l of
pr o pa no i c ac id a nd 1 .00 mol of s odi um pro pano a t e .
I t i s c ont a mi na t e d by t he a dd i t io n of 100 cm3 of
1 . 0 M hydro chlo r i c a c i d . Ka for pr op an oic a cid i s
1 . 30 x 10- 5 mo l dm- 3 . Cal cu lat e :
(a ) the pH of th e unc o nta minat e d buffe r s o l ut i o n ,
(b ) t he c han ge i n pH ca us e d by t he addit ion of hy dr oc hl or ic
aci d .

Solu t i o n
(a ) Cal cul at e a s i n pre vio us exerc ise s .

[ H+(aq )] = K [ HA( a q )] 0 . 500 mo l dm- 3

1. 30 x 10 - 5 mo l drn" ? x 3
a [A (a q )] 1 . 00 mo l dm
6 . 50 x 10 - 6 mol dm- 3
pH = - lo g[ H+ (a q) ] = ~
(b) (i ) Calc ulate th e amoun t of hydrochlo r i c ac i d a dde d :
n = c V = 1 . 00 mol dm- 3 x 0 . 100 dm3 = 0 . 100 mo l
(i i ) Ca l c ul a t e the amounts of pr o pa noa t e io n an d pro pa noi c acid a f t er
a ddi ng hydroc hloric acid by r e f e r e nc e to t he e qua ti on :
H+( aq) CH3C H2C02 - (aq) ~ CH 3CH2[0 2H( aq)
+

Assume tha t all o f t he ad ded hydro gen i o ns rea c t s o th a t :

a mount of pro pa noate i o n af ter r ea c t io n =
i ni t i a l amount - amo unt re a cted = ( 1 .00 - 0 .100) mol 0 . 900 mol
Amo unt of pro pan oi c ac id aft e r r e a c ti on =
i ni ti al amount + amount fo r med = (0 . 500 + 0 . 100 ) mo l 0 . 600 mo l
Thes e amo unt s ar e t he new eq ui l i br i um a mo unts .
(i i i ) Sub s t i t ute t he s e new va l ue s i n t he e xpres sio n fo r [ H+(aq ) ] you
ha v e a l r ea dy de ri ve d .

[ W (aq ) ] K [ HAl aq )]
a [A f eq l ]
1 . 30 x 10 -
5
mo l dm-
3
x ~ : ~~~ ~~ ~j~
8 .67 x 10 - 6 mo l dm - 3
( iv) Calcula te t h e pH .
pH = -l og[ W ( a q J] = - 10g e8 . 6 7 x 10 - 6 ) = -6 + 0 . 93 8 = ~
(v) Compa r e th is wit h t he ans wer t o pa r t ( a) ; no t e t ha t th e pH ha s
c ha nge d by 5 .06 - 5 .19 = -0 . 13 uni t s ; i . e . the pH ha s decre a s e d
by 0 .1 3 pH unit .

Now t ry two s imi l ar pro bl ems .

67
Exercise 52 Calc ulate the change i n pH of 100 cm3 of a buffe r
so l ut io n containi ng 0 .50 mo l dm- 3 of e th an o ic a ci d a nd
0 .50 mo l dm- 3 of potass ium etha noa te when i t i s
co nta minate d by :

(a ) 1 . 0 cm3 of 1 . 0 M hydr o c h l o r i c a c id ,
( b) 2 .0 cm3 of 1 . 5 M po tass ium hydr o xi de .
K ( CH 3C0 2H ) = 1 .7 0 x 10 - 5 mo l dm - 3
a
[ Ans wer s o n page 101 )

Exe r c i s e 53 A buffe r sol utio n i s pre par ed , con ta i ni ng 2 . 0 mol dm- 3 ~

of b ut a no ic aci d a nd 0 .50 mol dm - 3 o f sodium b ut a noate .
Ka f or bu t an oi c ac id is 1 . 5 X 10 - 5 mo l d m- 3 • ~~

( a) Cal cul a t e t he pH of t he unco ntam inated buffer s ol uti o n .

( b) Ca l culat e the c hange in p H whe n 1 .0 dm 3 of th e bu ffe r
s o l ut io n is con t a mi na t e d by t he additio n of 20 c m3 of
2 .0 M s odium hydr ox i d e s o lut i o n .
( c) Ca l c ul a t e the c hange i n pH when 1 .0 dm 3 of t he s a me buf fer
solu tion is con t aminated by the a dd i t ion of 100 c m3 of
0 .5 0 M hydrochlor ic aci d .
( Ans we r s on pag e 101 )

I f yo u wou ld li ke e xt r a practice wi th th is type of c a l c ul a t io n, t ur n t o

Appe nd i x 1F o n pag e 87 .

Afte r doing t he s e exe rc i ses you s hould ha ve some i d e a o f th e amou nts of a c i d

and alkali a b uffe r sol ution c a n abso rb , wit ho ut a ny significa nt change in
i t s pH . To compare what happens when pure wa t er i s c onta mi nated with ac id o r
al ka li , try t he ne xt exerc ise , in which th e same amo unts of ac i d and a lka li
as i n Exerc ise 52 a re ad ded t o th e same volume of wa t e r .

Exe rc ise 54 Calc ulate t he cha nge in pH of 100 c m3 of pure wate r

whe n
[a ) 1 .0 c m3 o f 1 . 0 M h yd r o c h l o r i c ac i d i s a dded ;
[b ) 2 . 0 cm3 of 1 . 5 M sod iu m hyd r o xi d e is ad ded .
[ Answe r s on page 104 )

Mo st calc ulatio ns a nd exe rc ises c o nc ern acid ic b uf fe rs , i . e . th ose ma de from

a weak ac i d a nd one of i t s salts . However , you sho uld a lso be a b l e t o
d iscuss bas i c b uf f er s , whi ch we co ns ide r i n t he nex t sec t i on .

68
Bas ic buffers

Ob jec t i ve s . Wh en YQU have fi nish ed th i s sect i o n , you s houl d be ab le to :

(35) wr i te a n e x pr e s s i o n f o r th e diss o c ia ti o n c o ns t a nt , K b , of a ba se ;

( 36) writ e a n e x pr e s s i o n r e l a t i ng t he ba s e di s s oc ia t i on const a nt , K to

b,
t he dissoc i a t i o n co nst a nt, Ka , of t he co nj uga t e a c i d .

As we men tion ed in Le ve l One, a weaK bas e and one of i t s salt s i n s o l ut i on

c a n be used as a buff er sy s tem . In s o l ut io n , a wea k bas e suc h a s ph e nyl -
ami ne , C6 Hs NHz , t e nds t o acce pt a pr o t o n to be c ome its co nj uga te a c id :
C6Hs NHz (aq ) + Hz O( l ) ? C 6H sNH ~ + ( aq) + OH -(aq)

Si nc e wa t er is presen t in e xcess , i t s c once ntra t i on ca n be r egarded a s

c o ns t a nt a nd we ca n c omb i ne i t with Kc to g i ve Kc x [H 2 0 (l ) J ~ Kb' t he
ba s e dissoc iat ion c ons ta nt . The exp r ess i o n t hen be co me s :
K ~ [ C6 Hs NH3 +( aq l] [ OW( aq l]
b [ C6 Hs NHz ( a q ) ]

Howe ver , sin c e a ny c a lcu lati o n o f pH involve s hydro gen i o n c o nc e nt r a t i o n a t

s ome poi nt , i t i s mo r e c o nv e ni e nt t o tr e a t th e sys tem i ns t ea d as a wea K ac i d
d is s oc i a t i ng and use K i n t he usua l way . The a bove s ys t em becomes :
a
C6HsNH 3 +(aq ) ? C6 HsN Hz(a q ) + H+ (a q)
K ~ [C 6HsNH z ( aq) ] [ H+( a q ) ]
and
a [C 6 HsN H ~+ ( a q ) J

Re me mb er i ng th a t Kw ~ [ H+( a q ) ] [ OH-( a q )] , you can s ee f r om the e x pre ssio ns

fo r Ka a nd Kb that Kb ~ 1/Ka x Kw '

To ma Ke s u re t ha t yo u ar e con fiden t wi t h thi s wa y of t reat ing ba s ic buf f er s ,

B
r ea d th rou gh t he ne xt WorKe d Exampl e an d try t he e xe r c i s e foll owi ng it .

Work ed Examp l e A buffer so lu ti o n i s prepar ed by ml xl ng 750 c m3 of

0 . 50 0 M phen y l met hy la mi ne , C6 HsCHzN Hz , a nd 250 c m3 of la!
1 .0 0 M ph e ny lme t ny lami ne hy dr oc hl o r i de, C6 Hs CHz NH3 +Cl - . ~
Assum i ng th at Ka f o r phen y l meth yl a mine hyd r o c hl o r i d e
i s 4 . 3 0 x 1 0 - ~ o mo l dm- 3 , ca l c u la te th e pH of the buf f er
solu ti o n .

So l ut i o n
1. Wr i t e a n eq ua ti on r e pres e nt in g th e e q ui l i br i um a s t he di s so c iat ion of
an acid .
C6Hs CH z NH 3 +(a q ) ? C6 Hs CHzNHz( aq ) + H+(a q )
2. Wri te an exp r es s io n f or Ka a nd rea r ra nge i t to gi ve a n ex pr e s s i o n for
[ W( aq) ] .

69
No te that this i s simply another example of the general equation :
[ a ci d ]
[ H+( aq ) ] =K a x [ c on j uga t e base]

3. Calc ulate t he amount of eac h s ubsta nce added :

n(C 6HsCHzNHz) = cV = 0 .500 mo l dm- 3 x 0 .750 mo l dm - 3 = 0 .375 mol
n(C 6HsCHzNH ~ +C I -J = cV = 1 .00 mo l dm- 3 x 0 .250 mo l dm- 3 = 0 .250 mol
4. Si nce Ka i s so smal l , assume th at these amounts are also the equ ilibrium
amounts , a nd s ubst itute t hem in the express i on f or [H+(aq J ] .
- [C H H +(aq J]
[ W( aq J J = K a x [C 6 sCHzN 3
6HsCH 2NH z(aqJ]

4 . 30 x 1o - ~ o mo
1 dm 3 x 0. 2 50 mo l/V
0 .375 mol/V
2 .87 x 10 - ~o mol dm 3

5. Calcu late th e pH
pH = - log[H +(aq ) j -10 + 0 .457

Now t ry a similar problem .

Exerc ise 55 Calc ulate the t he pH of a buffer sol utio n ma de by mi Xin g~

750 cm3 of 0 .20 M a mmoni um ch lori de a nd 750 c m3 o f
0 . 10 M ammo nia so luti o n . As su me that Ka f or the ~~
ammon ium ion is 6 .00 x 1o - ~o mol dm- 3 •
(Answ er on page 102 J

The relationship between pH) Ka and composition of a buffer

Obje c t ives . Whe n you have fi ni s hed this sectio n , yo u sh o uld be able to:

( 37 ) derive an expression rel ati ng pH, Ka a nd composition , for a buffer

s ol utio n;
( 38 ) c a l c ula te the c ompositio n o f a buff er of know n pH.

You hav e now lea r ned how to do seve ra l types of calculation on buffer systems ,
ba se d o n the expressi on for t he ion izat ion cons tant of a weak acid :
K - [A-(aqJ] [ W(aq )]
a - [ HA( aq) ]
It is oft en co nve nie nt to us e a loga rithmi c f orm of t his exp ressio n wh e r e
-log[H +(aq ) ] can be r e pla c e d by pH a nd - log K by pK .
a a
The express io n is similar i n fo rm to the one you derived for an indi ca t or on
page 50. In th e next exe rcise you der ive the expressio n f or pH of a buffer
co ntai ning the weak acid , HA.

70
Exe r c ise 56 Fo r a b uf fe r s o lut i o n ma de f r om t he we a k a c i d, HA , a n d
a s a l t , Na +A- , d e r i ve th e r e l a t i o n s h i p :

[ HA( a q ) ]
pH = pKa -l o g [ A ( a q J]

(A nsw e r o n pa ge 10 2 )

Th e equat i o n yo u ha v e ju s t d eri ved i s us e f u l f or c a lcu lat i ng t he compos it ion

o f a b uff e r f r om i t s pH . In o t her wo rd s , i f you wa nt t o mak e up a b uf fe r
of a pa r tic u l a r pH; k no win g pKa fo r t he wea k a c i d, the eq uatio n a l lo ws y ou
to c a l c u l a t e t he r a ti o of co nc e nt ra t i o n s o f a c i d to c o nj ug ate base that you
wo u l d nee d .

Calculating the composition of a buffer from pH

Th i s c a l cu l a t i o n t a kes two mai n f orms . We no w go t ho ug h t he s e , g iv i ng a

Wo rke d Exampl e fo l low e d b y a n e x e r c i s e i n each c a se .

Wo r ke d Exa mpl e In wha t pr opo r t i o ns mu s t 0 . 0 20 M so l ut io ns o f b enzo i c

a c id , C6 H5 C0 2H , an d s o d i um u e nz o a t e , C6H 5 C0 2 Na , b e
mix e d t o g ive a bu f fe r s o l ution o f p H 4 .57 Ka f o r
b e nz o ic ac id i s 6 .4 x 10 - 5 mo l d m- 3 •

So l u t i o n
1. Fi r s t c a lc u l a t e pK f o r be nzo i c a c id .
a
pK = - lo g K = - l o g ( 6 . 4 x 10 - 5 ) = - (- 5 + 0 .80 6 2 ) = 4 . 2
a a
2. Wr i t e do wn t he e xpr essio n f o r th e pH o f t h is b uf fe r so luti on :

H= K - 10 [C 6H 5C 0 2 H( aq J]
p p a g [C 6H 5C0 2 (aq )]

As y o u ha v e sh own i n Ex e rc ise 56 , th i s ex p r e s s i o n i s d e r ived f ro m the

e q ui l i br i um l a w exp r e s s i o n , i n t hi s cas e fo r ben zoi c aci d . I f yo u c a nno t
r e me mb er it, i t t a ke s o n l y a few mo me nt s to d er i ve i t .
3. Sub sti t ut e t he k no wn val ue s of p H a nd pK i n to t he exp re ssio n f o r pH.
a
4 5 = 4 2 - log [ C6 H5 C0 2 H( a q J]
. . [ C6 H:>C0 2 ( a q ) ]

l og [ C6H5 C0 2 H(a q J) = 4 .2 - 4 . 5 = -0 .3 = -1 + 0 .7
[C 6 H5 C0 2 ( a q ) J

[C 6 H5C 0 2H ( a q ) ] t Ol ( 1 0 70 ) ~
O 5
i C H C0 ( a q)] = an 1 0 9 - + . = ~
6 5 2

4. Si nc e K i s s mal l , a s s ume t h at t he e qu i l i br ium a mount s a re t h e s a me a s

a
t he a d d e d amo u nt s .
Th e n t h e mi xt ur e sh ou l d be mad e i n t he p r o po r t i o ns o f one vo lu me of
0 . 0 2 M be nzoi c ac i d t o t wo vo lume s of 0 .02 M sod i um b en z o a t e .

71
Exerc ise 57 I n wha t ra tio must 0 . 50 M s o l ut i o ns of ethanoi c ac i d a nd ~
s odi um etha noat e be mix ed to pro d uc e bu ffer s oluti ons o f :
(a) pH 4 .7 0 , ( b) pH 4 . 4o ? ~~
pKa ( CH 3C o zH ) = 4 .74
( Answers o n page 102

Wo r ked Exampl e A bu f f er o f pH 3 .50 is to be ma d e b y a ddin g s o d ium

iodo ethanoate , ICHzCoz- Na+, t o 0 . 50 M i o doe t ha no i c
acid , ICHzCO zH. What co ncentration of s odi um i o do -
et ha noate i s needed?

So l ut i o n
I n th is Wo r ked Example , we aga in ma ke th e a ssumpt i on that b eca use the
dissoc ia t ion of io do eth anoi c ac id i s sma l l , we ca n t ake initia l c o nc e nt r a t i o n s
a s equa l t o e q ui li br i um c o nce ntrations .
1. Write down th e e xpr e s s ion for th e pH of t his buffer s o l ut i o n :
[ I CH zCo z H(a q )]
pH = PK - 1 0 g 7-=::::-;-:=-:::::-::::-=-~---'-7-f-
a [ I CHz Co z (a q)J
2. Let th e conc entratio n of sodi um i o do e t ha noa t e be x a nd s ubst i t ut e t hi s
a nd t he va lue s for pH a nd pKa in to the equa tion :

3 .50 = 3 .17 - log 0 .5 0

x

3. Re a r r a ng e t he e q uat i o n ; us i ng t he r ela tion log a

lo g a - log b
b
3 . 50 - 3 . 17 - l og 0 .50 - ( -log x )
0 . 33 -lo g 0 . 50 + l o g x
l og x = 0 .33 + ( -1 +0 . 69 90 ) 0 .33 + ( - 0 . 30 1) 0 .029
x = a nti log 0 .02 9 = 1 . 069 = 1 . 07

t he c o nce nt rat i o n o f sodi um iodo e thanoate nee de d i s 11 . 0 7 mol dm- 3 !

Exerc i se 55 What amount of s od i um me t ha noa t e , HC0 2 - Na ' , must be
a dded pe r dm 3 of 0 .50 M s o lu t i o ns of metha no i c a c id ,
HC0 2 H, to prod uc e buffer sol ut i ons of
(a ) pH 3 .5 , ( b) pH 4.n
K (HCO zH) 1 .58 x 10 - 4 mo l dm- 3
a
( Ans wer s on page 10 2 )

I f yo u wa nt more pra c ti c e a t t hi s ty pe of c a l c u l at i o n , see Appe nd ix 1G on

pag e 88 .

I n th e next exe rc ise you are rem inded of th e vit a l rol e o f buffe r s i n
b iol og i c a l systems . No t ice t hat the expr es s ion g i ven f or t he pH is no t
qUi t e th e sa me as t he o ne you ha ve us ed so fa r . However , t he t wo forms
are e quiva le nt be c au se
1 [b as e ] [ ac Ld ]
og [ a C lid JI - l og i'-;-----T
[ ba s eJ

72
Exe r cise 59 I n a buffer ed s o lu tio n ,

pH = - l og K + 10 [ba s e ] e qm
a g [ acid ] eqm
Huma n pla s ma i s buffe red ma in ly by dis s o l ved c a rb o n di o xi de
which has r ea c t e d to form ca r bonic ( I V) acid :
H2C0 3(aq) ~ H~ ( aq ) + HC0 3 -( aq)
(a) Ex pla i n how carbon ic ( I V) ac i d can buffer human plasma .
Give an example t o i l l u s t ra te yo ur an s wer .
( b) Whe n th e c onc e nt r a t i o ns of c a r boni c (I V) a c id and hydro ge n-
c arb o nate ion a re e q ua l , t he c o nc en tra t i o n of hy dr oge n i o n
is 7 .9 x 10 - 7 mo l dm- 3 • Ca l cula te t he va l ue of lo g K f or
ca r bo ni c ( IV ) a cid . a
(c) Usually th e pH of human plasma i s about 7 . 4 . Calcu la t e th e
ra t i o o f the c onc e nt r a t i ons of hydrogen carbona te i o n a nd
carboni c(I V) a cid in p l a s ma .
(d ) I f th e total con ce nt rat io n of hydroge nc arbo na te io n and
carbo nic(IV ) aci d was eq ui vale nt to 2 .52 x 10- 2 mo l dm- 3
of ca r bo n diox i de , ca l cu late the sepa rate con c e nt ra t i o ns
of the hydroge ncarb onate io n a nd t h e ca rb o nic( IV ) a cid i n
p l a s ma .
( Ans wers on page 103 )

Now we con sider how best to c hoos e s ub st a nce s to ma ke a b uff er so lu t io n of

a pa r t icu lar pH.

Choosing substances for a buffer solution

Ob j e c t i v e s . When you ha ve f i nis he d t his se ctio n , you sho ul d be ab l e to :

(3 9 ) make a sim pl e buff e r s o l ut i on a nd tes t i t s buffering ca pa c i t y ;

(40 ) ex pla i n wh y a buffer s ol ut i on ge ts l e ss eff e c ti ve a s it i s di luted .

As you know, when a c id i s a dde d to a bu f f e r so lu t io n , the hyd r oge n io ns re a c t

with t he co njugate ba se acc ordi ng t o t he g e ne r al e qua t i on :
H ~ Caq) + A-Caq) ~ HACa q)
a nd when ba se i s a dded , t he hydro xide i o ns r ea c t wi t h t he ac i d :
OH- (aq ) + HA(aq) ~ A-( a q) + H20CI )
The r ef or e , an e f f i c i e nt b uffer sy st e m, eq ua l l y r esistan t to bot h a cid a nd
ba se co nta mi nat i on , wo uld ha v e equa l c o nc e nt r a t i o ns of wea k ac i d an d
co nj uga te ba s e , i. e . [ .HAC aq )j = [ A- Ca q J] .
Subs t i t ut i ng in the exp r e ss ion fo r pH of a bu f f er :

pH = pKa -l og t ~A ~:~~ ] = pK a - l og 1 = pKa

There fo re , a buff e r i s at i t s most effect i ve at t he pH eq ual to t he pKa of t he

a c i d . In pr a c t ice , t he a c i d to be us ed s hou ld be chosen s o t ha t the re q ui red
pH fal ls wi th i n 1 pH uni t e i t he r s i de of t he pKa va l ue , i . e . pKa ± 1 .

P3-0
73
Now se e whet he r you can apply th is idea to find s uitable substances fo r maki ng
up buffe rs of a pa rt icular pH va lue by t r ying th e next ex ercise .

Exe rci se 60 Use yo ur book of da t a to f ind s ui tab l e weak aci ds a nd

co nj ugate bas e s t o make up buffe r s olut ions of the
fo l l owi ng pH va l ues :
(a) 10 . 0 (b) 9 .0 (c ) 7 .0 (d) 5 .0
For eac h on e , sta te t he weak acid , the conju gate base a nd the
pKa va lue of the a cid .
(Answe rs on pa ge 103 )

In Experiment 7 , which fo llows , you put your knowl edge of ca lc ulat i ng

t he compos i t ion of a b uffe r s ol ut io n of known pH int o pract ice .
tLlJ1 \
~

EXPERIMENT 7
Preparation of buffers : test ing
t he ir buffe r i ng capaci ty and the
effec t of d i lu t i o n

Ai m
The purpos e of this exper i ment i s th r e ef ol d :
1. t o prepa re t wo buffer solut ions of
pH val ues of 5 .2 and 8 .8 ;
2. to check t he pH a nd buffer i ng capacity
of th e pr e pa r ed buff e r s ; < :.~.
i • lilt

3. t o examine t he e f f e c t of dilu ti on o f the

prep ared b uffe r s o n t heir pH a nd
.,
buffe r i ng capac i ty .

I nt ro duc t i on
Thi s expe r iment lends itse lf to a pla nni ng exerc is e where yo u have to work
ou t f or yourse lf the detailed pr oc edu re on the bas i s of t he hi nt s given below .
When you ha ve worked o ut t he deta i ls , check with your t ea c her t hat you r
proposa ls are se ns i ble and th a t a ppa ra tus wi l l be avai lab le at a su it ab l e
ti me. Try not to wa ste l a bo r a t o r y t i me on pla nn ing !

Hint s
1. The f ol low i ng s ol ut io ns wi l l be ava i la ble :
ammo ni a so l uti o n, 1 .0 M NH3
e th ano i c a c id , 1 .0 M CH3C0 2 H
ammon ium chl oride s ol ut i o n, 1 .0 M NH 4C l
s odium ethanoate s o lut ion , 1 .0 M CH 3C0 2Na
2. Us e th e e quat i o n on page 71 t o ca lc ula te how mu ch of the ab ov e so l ut ions
yo u need to make 100 cm3 of eac h buffer .
3. Yo ur experi ence of Expe r i me nt 3 wi l l be ver y u s e f ul.
4. For the dilut ion e f f ect , tr y di l ut i ng yo ur bu ffer to 1/ 10 and 1/ 100
of it s i nitial c on centrat i o n .

74
5. Prepare a s ui t a b l e tabl e to r ec o r d yo ur r e s ul t s . This sh ould be hand ed
to your teac her wit h yo ur answers to the qu e s tio n s be low .

Ques t -ions
1. \'-'ha t di d you us e t o make 100 e rn " of a buffer of pH 5 .2 ?
2. What d id yo u use to make 10 0 cm3 o f a bu f f e r of pH 8 .8 ?
3. How c l o s e to the req uired va lues were the measured pH va l ue s of yo ur
pre pared buffers?
4. Desc ribe t he e ffect of dilution o n t he pH of yo ur prepared buffe rs . Was
t hi s effect e x pe ct e d ?
5. Des cri be t he effect o f di luti o n o n t he bUfferi ng capac ity of you r pr ep a r e d
b uffers .
6. Suggest a reas on fo r the pH 8 .8 buffer be i ng l ess sta b l e ov er a pe riod of
t ime t ha n many ot her buffer s .
(An swers on pa g e 104 )

Buffers and dilution

The oret ical ly , dil utin g a buff e r has no effe c t on t he pH beca use bo th th e
c o nc e nt r a t ion o f wea k aci d a nd i t s co nju gat e bas e a re red uc e d t o the same
e xte nt .

For e xample , suppose a buffe r mad e f rom 0 .1 M acid and c onj uga te base is
dil ut ed a hund red t i me s , t he l og term i n th e e xpre ss io n f or pH i s unch a nged
s ince :
0.1 0 . 00 1
log ~ l og 0 . 001 = 0
and the pH theo retical ly r e ma i ns equal to pKa . I n pra c ti ce , a s yo u have f o und
out i n Expe ri ment 7 , the pH does change slig ht ly with dilution . This i s
bec a use the equa t i on you der i ved i s an ap proximat io n .

Howeve r , dil u t i o n has a ma rke d e f f ec t on buffe r ing ca paci t y , a s you ha ve also

noti c e d i n Experi ment 7 . BUffe r i ng c apa city de pe nds on the a mo unt s of we ak
acid and conj ugate base in so lut ion . The mor e c o nc e nt rated the s e are , the
great er wil l be t he bu ffer ' s a bility to co pe with co ntaminatin g a c i d an d base .

Now try t he ne xt e xerc ise , whic h t est s what you have l e a r ne d a bo ut buffe r
so l ut io ns .

75
Exercise 6 1 The t able shows the resul t s of meas ur e me nts of th e pH
values of s ome s o l ut i o ns before an d aft er t rea tme nt wit h
an equal volume of 0.01 M sodium hyd ro xide solution .
0 '

pH befo r e pH afte r
Experi ment Ori ginal solution a dd i ti on ad di tion

A 0.01 M ethanoic aci d 3 .4 8 .2

0. 1 M eth anoic aci d +

B 4 .8 5 .0
0 .1 M sodium et ha noa t e

C 0.1 M s odium et hanoa t e 8. 4 11 . 7

0 Pure water 7.0 11 . 7

(Ethanoic aci d is a cetic acid and sodium ethanoate i s

sodium acetate. )
(a) (i) Whi ch of t hese fo ur li quids i s a b uffer solution?
( ii) Wha t ha ppened to the oH-(aq) ions when t hey were
adde d to this sol ution?
(b) Why does s odi um etha noate NO T have a pH of 7?
(c) What woul d be the final pH of t he mi xt ur e B if it had
been di luted with an equal volume of water in stead of
the al ka li ?
(d) ( i) Calcul ate the co ncentration of hydro gen ion s in
0.01 M ethanoic aci d .
(ii) St a t e the conc entration of e tha noa t e ions in
equili brium with the hydro gen io ns in 0.01 M
etha noic acid.
(iii) Calculate Ka , the diss oc i atio n const ant for ethanoic
acid .
(e ) Name a pair of c hemi c a l s suitable f or the preparation of a
buffer solution of pH in the range 9- 11 . (Us e your data
book . )
(Answer s on page 104 )

In the
buf fer
a weak
next experiment , yo u ma ke use of th e e quatio n for the pH of a
s o l ut i o n i n order to determine the ioni zation constant , Ka , of
acid . You also us e your knowled ge of indicators, and the
lID1
met hod is very similar to Ex periment 5, to which you s ho ul d r efer .

76
 EXPERIMENT 8
De ter mining the di s soc iat i on c o nstant
of a weak a c i d us i ng an i nd ica t or

Aim
The pu r po se o f the e xp er iment i s to pre par e
a b uffe r s o lu tio n f rom be nzoic a ci d an d
s o di um ben zoat e, an d t he n to de termine i t s
p H by a v i s ua l met hod a s us ed i n Exp e riment
5 (pag e 52 J . pKa for t he ac i d can the n be
ca l c ulated fr om t he pH by the usu a l buf f e r
fo rmul a .

In t r oduc t ion
Fir s t yo u prepar e a buffe r s o l ut i o n f ro m benzo ic ac id an d sod ium be nz oa t e .
Then yo u mea s ure i t s pH us ing t he same pro c e d ur e as i n Expe r ime nt 5 on
page 52 . Ha v ing determi ned t he pH, yo u ca l c ula te Ka f or ben zoi c a c i d usin g
the equat i o n :
[ C6H5C02H( a q J ]
pH = pKa - 1 og
[C 6 H5C02 ( aqJ]
Ask you r tea cher which of the tw o met hod s you shou ld use , but a ga in rea d the
i ntrodu c tio n f or bo t h methods on pages 52 t o 53 .

Re qu irements - Me th od 1
s a f e t y spec ta c les
ben zoic ac i d so l ut i on , 0 . 020 M C6 H5 C02 H
s od i um benzoate so l u t i o n , 0 .0 20 M C6 H5C02 Na
meas ur i ng c yl inde r , 10 c m3
20 t est -t ubes
rac k o r r a c ks t o ho ld 2 rows of 9 t ube s ea c h
bromop he no l blue so l ut i on
2 t ea t pip e t t es I ~I
hyd r oc hl or i c acid , c o nce nt r a t e d, HCl - - - - - - - - - - - - - - - - - - f t
s t i r r i ng r od
s o di um hydro xid e solu t io n , 4 M Na OH - - - - - - - - - - - - - - - - - - •~i ,
di s t i ll e d wat er .1:11. _

Req ui r e me nt s - Met hod 2

sa fety s pec tacl es
be nz o i c ac id so l ut i on , 0 . 020 M C6H5 C02H
s odium be nzo at e so lu t io n , 0 .020 M C6H5C02Na
measu r ing cy l inde r , 25 c m3
beake r , 100 e rn"
2 be ake r s , 25 0 c m3
hy droc hl or ic a cid , 0 . 1 M HCl
bromophe no l bl ue s ol ut i on
Bj e r ru m wedge
sti r r i ng rod
so d i um hydroxid e so lu t i o n , 0 .1 M NaOH

77
 Pr ocedure - Metho d 1
1. Pre par e a buffe r so lut ion by mlx l ng 5 .0 c m3 of 0 .020 M benzoi c ac i d a nd
5 .0 cm3 of 0 .020 M so d i um benz oa te i n a test - t ube .
2. FOllow t he pr oc e dure for Me t hod 1 o f Exper iment 5 on page 54 . In
ste p 5 , us e the b uffe r you have j ust pr e pa r ed .

Pro c edure - Me t hod 2

1. Pr e pare a b uf fe r s o l ut i on by ml xln g 12 . 5 cm3 o f 0 .0 20 M be nz o i c a cid
and 12 . 5 cm3 of 0 .0 20 M s od i um be nzo a t e i n a smal l be a ke r .
2. Fo ll ow t he pr oced ure f or Method 2 of Exp eriment 5 on page 5 4 In
ste p 3 , us e t he buffer yo u ha ve just prep ared .

Cal cu l ation - bot h me th o ds

1. Obt a i n t he pH of t he buffe r sol ut i o n by a ub s t Lt ut i ng i n the e qua tion :
_ _ [ HIn ( a q ) J
pH - pKI n log [ I n ( a q )J
2. Obt ain pKa , a nd he nc e Ka , by s ubst it ut i ng i n t he eq ua t i o n :
C H C0 H( a q ) )
pH = pK - 10 0- [ 6 5 2
a '" [C 6 H5 CO 2 ( aq ) )
(Spec i men r esul ts on pag e 10 5 )

Now t hat yo u ha v e compl e t ed your s t udy of bu ff er s o l utio ns , you

s hould attempt t he f ollowing Tea ch er -ma rk ed Exe r c i se . Che c k
throu gh yo ur no t e s o n buf f e r s an d t hen g i ve yo urs e l f a bo ut 40
mi nute s (i ncl udin g plan ning t i me ) to wr ite t h e a ns wer .

Te a c he r - ma r ke d
Exercis e
Wi t h what sub sta nces , ot he r t ha n potassi um hy dro g e n
pht ha la t e , c ou ld you ma ke a bu f fer s o l ut io n o f
pH 5 . 6? Pr e par e a se t of in str uc t io ns s u i t a ble f or
0
a s i xt h -fo r m s t ude nt for t he pr epa ra t i on of 1 dm3
of such a s o l ut i o n . De scri be how yo u c o ul d che ck t he
pH of yo ur b uf fe r s o l ut i o n using a si ngle i nd icato r .

78
END-Of-UNI T CHECKLIST
You have now r eac hed t he e nd of thi s Uni t . I n ad dition t o wh at was l i s t ed
at t he en d of Leve l One , you sho uld now be able t o :

(24 ) & ( 26 ) exp l ain qualit ati vel y how a n ac id - base indi cat or works,
a s s umin g i t to be a weak a c id ;
( 25) & ( 27) ex pl a in how th e pH r a nge of a n ac id - bas e indic a tor is related
t o KI n' the equi l i br i um c onstant f or i t s d i ssoc ia t i o n;
( 28) des cri be a vi sual me t hod fo r determin in g KI n fo r an ac id -b a se
indicator;
( 29 ) s ketch the general s ha pe of fo ur t ype s of pH curv e whi c h s how how
pH chang es during th e co urse of t it r a t i o ns ;
(3 0) choose suitab le acid-ba s e indicators for various ti tra tions, e xpla inin g
your choice by r ef ere nc e t o pH curv es ;
( 31 ) describe how a sa l t af fec ts t he pH of its s ol ut ion i
(32) ex plai n why t here i s a small cha nge i n pH f or r el ativ el y l arge
addition s of alka l i i n certa i n r eg io ns on a t it rat i o n c urve i
(33) ca lc ula t e the pH of a buffer s olu t i o n;
(34) cal cula t e th e c ha ng e i n pH t hat t ak es plac e when a bUff er is
contami nated by the add i t i on of a cid or al ka li ;
(35) & ( 36) writ e an expression for th e dis sociatio n co nsta nt , Kb , of a
bas e a nd s how how i t is rel at ed to t he di s socia tion con s t a nt ,.
Ka , of the c onjugate ac i d j
(37) derive an exp re s s ion r e l a t i ng pH , Ka and c omposit ion , fo r a buff er
sol ution;
(38 ) ca l culat e th e c om pos ition of a buffer of known pH;
( 39) ma ke a simpl e buff er s olutio n and te st it s buffe rin g ca pa c i ty ;
(4 0 ) explain why a buf fer sol ut i on ge ts le s s effe c t i v e a s it i s dil uted .

Check that you have ad equ at e no tes b efore go ing on to th e End -of - Unit Test .

END-Of-UNIT TEST
To f i nd o ut how well yo u hav e lea r ne d t he ma te r i al in t his Unit , try
t he t e s t which follo ws . Read the no t e s below before sta rting .
?J
1. You should s pend abo ut 1~ hour s on t his t est . ~
2. Ha nd yo ur answers to yo ur te acher f or mar kin g .

79
END-OF-UNIT TEST
1. I n which of the fo l lowi ng reaction s has the na med substance NOT
acted as an acid ?
hydroge ns ulphate
i on
B NH 4 +(aq) + NaNH 2(s) ~ Na +(aq ) + 2NH 3(g) ammon ium i on
C Mg 3N 2(s) + 6 H20(I) ~ 3Mg ( OH)2 ( S) + 2 N H~ ( g ) water
o CaC03 ( s ) + 2CH3 C0 2 H( a q ) ~
Ca 2 +(aq ) + 2CH 3C0 2-(a q) + CO 2(g) + H2 0(I) etha noic ac id
E NaH(s ) + H20(I ) ~ H2(g ) + Na +(aq ) + OH-( aq) sod ium hydri d e (1)

2. Wha t is t he app rox imate pH o f a bu f f er so lu t io n contai ni ng

0 .20 mol of a weak mo noba s ic a cid (K a = 10- 4 ' 8 mo l dm- 3 ) an d
0 .20 mo l of t he s od i um s alt of th e a cid i n 1 d m ~ of a queous
sol ut io n?
A 2 .8 B 3 .8 C 4 .8 o 5 .8 E 6 .8 (1)

In Quest io ns 3 t o 6 inc l us ive , one , or more than one , of t he suggested

ans wers ma y be correc t . You should answer a s foll ows :
A i f o nly 1, 2 and 3 are correct
B i f o nly 1 and 3 a re co r r ec t
C i f onl y 2 a nd 4 a r e correct
0 i f on l y 4 is co r rec t
E i f some ot he r r es pons e , or combi na tio n , is c o r rec t .

3. For which of the fo l l owi ng pa i rs i s t he f i rs t speci e s the

co nj ugat e ba s e of t he seco nd ?
I II
1 CH 3 CHN H2C0 2 H CH 3 CHN H3 +C0 2 -
2 C6 Hs NH 2 C6H sN H3 +
3 HP0 4 2- P0 4 3 -
4 N0 2 - HN0 2 ( 1)

4. The i o ni z a t i o n constant f or wa t er has the values of

1 x 10- 1 4 mol 2 dm- 6 a t 25 °C a nd 1 . 7 x 10- 1 4 mo l 2 dm- 6 a t 7 5 ° C.
From this , i t may be deduced t hat :
the pH of water a t 75 ° c i s equa l t o tha t a t 25 °C
2 water i oni z es mo re at 75 ° c than at 25 ° C
3 a t 75 ° c water contains more H+ io ns than OH - i on s
4 the i o ni za t i on o f water is an endothermi c process ( 1)

P3- E
81
5. An indicator, X, is an acid with a dissociation constant (K a ) of
10- 9 mol dm-~. In aqueous solution, undissociated X gives a
yellow colour while the anion derived from it is blue.
Which of the following statements is/are correct?
In a solution of pH 1 , the indicator is yellow
2 In a solution of pH 7, the indicator is blue
3 In a solution of pH 9, the indicator is green
4 The indicator would be suitable for titrating a strong acid
against a weak base ( 1)

6. Mixtures which, when dissolved in water, act as buffer solutions,

include:
1 HN0 3 and NaN0 3 3 CH~C02H and NaCl
2 NH 3 and NH 4Cl 4 NaH 2P0 4 and Na2HP04 (1)

For Questions 7 and B, choose an answer from A to E as follows:

A Both statements true: second explains first.
B Both statements true: second does not explain first.
C First true: second false.
0 First false: second true.
E Both false.

First statement Second statement

7. The first dissociation constant
of a weak dibasic acid is always
larger than the second.
The transfer of a proton from a
negative ion to water is always
more difficult than the transfer
of a proton from a neutral molecul e
to water. (1)

B. In the chlorine molecule, the The concept of oxidation number can

oxidation number of the element only be applied to ionic compou nds .
is zero. ( 1)

9. (a) Give the Br~nsted-Lowry definitions of acids and bases. ( 2)

(b) Complete the follOWing equilibrium equations and identify the

acid-base conjugate pairs. In this context, state symbols such
as (aq) and (1) may be omitted.
(i) CH 3C0 2H + H20 ~ ( 2)
(ii) ~ OH- + NH 4 + ( 2)

(iii) + H- H2
~ OH- + (2 )

(c) Write an equation to account for the presence of chloride ions

in a solution of dry hydrogen chloride gas in pure ethanoic
acid. (2)

82
10. (a) (i) The dissociation c ons t a nt of propanoic acid
(C 2H5C0 2H ) is 1 . 26 X 10 - 5 mo l dm- 3 (i .e .
10 - 4 ' 9 mo l dm- 3 ) . Calcu late the pH of 0 .1 M propano ic ac id .
C2 H5 C0 2 H( a q ) ? C2 H5C0 2 - (aq) + H+(aq )
(i i ) Wha t is the hyd r o xide i o n co nc en t ra t io n of this sol ution?
(iii) What is meant by a buff er s olu tion?
How many mo l e s of potass ium pro pan oate must be added to
1 dm 3 of the 0 .1 M propanoic a cid in (i) to make a solution
of pH 5?
Would the resulting solution be a buffer solution?
( iv ) Pi cric a ci d, d i ssoc i a t io n c onstan t 5 .0 x 10- 3 mol dm- 3
( i . e . 10 - 2 ' 3 mo l dm- 3 ) , ca n act as an ac i d - ba s e i ndi cat or, the
indicator anions being r ed , and th e fre e acid yel low. What
colour would i t show in a so l uti on of pH 5? (9)

(b) My book of data li st s the a cid dissociation co ns t a nt of th e

ammonium ion as 6 .3 X 10- 1 0 mol dm- 3 ( i.e . 10- 9 • 2 mol dm- 3 ) :
NH4 +( aq ) ? ~ +(aq) + NH 3 ( a q )
From this , cal cula t e the equilibrium constant fo r the following
equili brium :
NH 3 (a q ) + H2o (l ) ? NH4 +( a q ) + OH-(a q) ( 2)

(c) The s ket ch shows how t he c o nd uc t a nc e va r i e s as a so lut i o n of

pot assium hydro xide i s added to 20 cm3 of 0 . 1 M HC l .

:: :-:r':'-'::r:'"....._.. ,.. t- - •
!- ;- ~
.: .
f .1.. ~
----:~.-.-!---~'--+------t--~----:-+--~-+--+-----+---l
; · '. 1 . • • ~ ~ -. ~ ! . . ..-.
I - " 1'''' · :. t · ~ ...
~ ~

i . t.. -.~~" i ... . . . ~ . i :- , : ~ · . : ~ ! : : .' __'..~~ :· 1.•.·_ :._ ':._~.'

t-- +....-. . _.-. - . . . ,i . -~·: ..:--:t:::-·:· 00 . . - -

; I' :" II>' . • ,~

-, t·
j'- " •
• !". ; .-- t -• •
_." l.
, ., ,i
-.
;_·i
• •

, • . '" 1 •• •
.. ··-:·-·-·· -T-~--~··~·--·-t---t---t----j-:-.-.-+--+---+---+-----:::
· , . , ~ . .. - . , • - • 1 " :>1
- I' I . . ,
...
1
, : : . : I:: : . • , j •.• ,

I
,
..
· . . ! . .. .
. . -,
· . . _o r
," ' - ' ..
. .. t ' ··
- --- - -i--......···_-···
. . ~ . :
! ... .
f i' .
· - - ·-·---..- ··-.. ·..-· ---~--t--·""""'f_=_o----4-t--_;_-__+--+_-_I
; . j . ~ . - I ·· .
, t .• , •
.
: . : I' . i ·
f l . , f' . ,- .
, - ~ • ~ .~... t . . • _ ,_ _ ·· ~· ··--r···· - .
. .. I " .
• ·4 • ••
.. I . . j . •
. . I
o 0.5 1.0 1.5 2.0 2.5 3.0
volume of KOH solution added/ cm 3

What is the co nc entra t ion , i n mo l dm- 3 , o f t he KoH s o lut ion ?

(K = 1 .00 X 10 - 1 4
mol 2
dm- 6
) ( 2)
w

Cont i nued ov e r l ea f .

83
11. (a) The indicator phenolphthalein may be regarded as a weak
monobasic acid, HIn. Expl a i n briefly why t he indicator is
coloured when the s olution in whi ch i t is present ha s an
excess of alkali. (2)
(b) The following is a curve s howing how th e pH changes whe n a solutio n
of 0.1 M sodium hydrO Xide is added to 20 cm3 of e t ha noi c a cid
during ti tration.

(i) What is the molarity of the ethanoic acid?

(ii) What is the pH of the solution in the titration flask when
12.5 cm3 of alkali has been added?
(iii) Calculate the dissociation constant, Ka , of the ethanoic acid.
(iv) Indicate by a sketch how the curve given differs from a possible
curve for the titration of 0.1 M sodium hydroxide again st an acid
of the same concentration as the ethanoic acid, but whose
dissociation constant is less than the ethanoic acid. (8)
(c) 1000 cm3 of a buffer solution has been prepared by dissolving
potassium hydroxide and methanoic acid (HC02H) in water. What
could be the effect on the pH of the solution of adding a further
100 cm3 of water? Give your reasons. (2)

12. Comment on the usefulness of the follOWing indicators in the titration

given in Question 11.
Phenolphthalein 9.0
Methyl orange 4.0
Bromothymol blue 7.0 (4 )

13. (a) A solution of methanoic acid, HC0 2H, has a pH of 2.23. Calculate
its c o nce nt r a t i o n . K = 1.78 X 10- 4 mol dm- 3 • (6)
a
(b) Calculate the pH of 0.0100 M dichloroethanoic acid, CHC1 2C0 2H.
K = 5.13 X 10- 2 mol dm- 3 • (7)
a
(Total 60 marks)

84
APPENDIX ONE

ADDITIONAL EXERCISES
Answe rs to these ex e r ci s es , t oge t her with a b bre vi a t ed me t hod s , a re on
pa ge s 105 to 108 .

A - Ca lculating pH fro mhydrogen ion concentra t ion

Exe rci se 62
What is t he pH of a sol utio n in which the hydro g en i on conce nt rat ion i s
8 . 34 x 10- 3 mol dm- 3 ?

Exe rci se 63
What i s th e pH of a soluti on i n whic h t he hydro ge n i o n co nc e nt rat i o n i s
2 .62 x 10 - 8 mol dm- 3 ?

Exercis e 64
Calc ul a t e th e pH of a 0 .54 M so lut i on of HN0 3 •

Exercis e 6 5
What i s t he pH of a s olut io n wh i ch ha s a hyd r ogen ion co ncen t r at i on of
2 .23 x 10 - 3 mol dm- 3 ?

B - Calculating hydrogen ion concentration f rom pH

Exe rci se 66
Ca lc ul a t e the hydro ge n i on conce nt r a t i o n of a sol u t ion wh i c h has a pH of 11 .1 1 .

Exercise 6 7
Wha t is t he h yd r og e n i o n concent rat i on of a s ol uti on which has a pH of 1 .11?

Exerc is e 68
Calc ula te th e hydro gen ion conc en t rat ion of a s o l ut ion whi ch has a pH of 5 .64 .

Exe r c ise 69
Calc ula t e t he hydr o ge n i o n co nce nt r a t i on of a s o lution which has a pH of 7 .7 1 .

85
C - Calculating Ka from concentration and pH

Exe rci se 70
The pH of 0 . 0 10 M et ha noi c ac id so l ut ion i s 3 .40 a t a par t i c ular temperatu re .
What i s th e dissoc i a t i o n co ns tant , K , of t he a c i d a t th i s t emp erature?
a

Exe rc ise 71
The pH of 0 .1 0 M methano ic ac i d ( HCO a H) i s 2 .4 0 . What i s the dissoc iat i on
c ons t a nt, Ka , of t his ac i d?
HCOaH ( aq ) ~ HCOa- (aq) + H+ ( a q )

Exerci s e 72
The pH of a 0 .10 M hydro g en sulp hid e so l ut i o n ( HaS ) i s 4 . 03 . Wha t is t he
dissoc iatio n constant , K , of the a c id ?
a
Ha S( aq ) ~ H+(aq) + HS-( aq )

D - Calculating pH from Ka and concentra tion

Exerc i s e 73
Wha t is the pH of a 0 .0 10 M s ol ut io n of chl oric(I ) ac id (hypoch lo rous a cid ) ,
HCl O?

Ka 3.7 X 10 - s mo l dm- 3

Exe rc is e 74
What is the pH of a 0 .010 M s o l ut i o n of bo r ic acid solution , H3B0 3?
H3B 0 3(a q ) ~ H+(aq ) + HaB0 3 -( a q)
K 5 .8 X 10- 10 mol dm- 3
a

Exe rcise 75
Wha t i s th e pH of a 0. 010 M hydr oflu or i c ac i d solut ion . HF?
HF(aq ) ~ H+( a q ) + F-(aq)
K 5 .6 x 10- 4
mo l dm- 3
a

86
E - Calcu lating the pH of a buffer solution

Exe rcise 76
A series of buf f e r s olutions was prepa re d f r om meth a noic ac id , HC02H, and
pot a s s iu m methanoa te , HC0 2 K, us ing t he fo llowi ng concen t ra tion s . Cal cul a t e
t he pH of e a ch bu ffer s o l ut io n . Ka fo r methano ic ac id = 1 .6 x 10- 4 mo l dm- 3 •

Solu t i on [HC0 2H J/mol dm- 3 [ HC 0 2K]/mo l dm- 3

Ca J 0 .10 1.0
Cb J 2 .0 0 . 20
(c 1 0 .50 2 .5

Exercise 77
What i s t he pH of a buff e r sol ut i on mad e fr om 100 cm3 of 1 .5 M a mmo ni um
c h l or i de a nd 100 cm3 of 0 . 60 M ammo nia ? Ka f or t he ammoni um i on i s
5 .6 x 1 o - ~ o mo l dm- 3 •

Exerc i se 78
A buff er so l ut ion is made by mlx l ng 500 cm3 of 2 .0 M so diu m di hy dr og en -
phosphate ( Vl , NaH 2 P0 4 , and 1000 cm3 of 0 .50 M di s odi um hyd rogenp hos pha teCV J ,
Na 2HP0 4 •
Ka f or t he di hydrogenphospha te (Vl i o n i s 6 .2 x 10 - 8 mol dm- 3 • Calc u l a te t he
pH of t he buf f er .

F - Contamination of buffer solutions

Exerc i s e 79
A buffe r s o l ut i on i s made f rom 1 . 0 dm 3 of 1 . 0 M e t ha noic acid a nd 1 . 0 dm3 o f
0 .5 0 M so diu m et ha noate . 200 cm3 of th is so lutio n i s pl a ced i n a bea ker .
Some on e acci de ntal ly mi xe s i nto t he buff er s o lut io n 10 cm3 of 1 . 0 M
hydr oc hl or i c ac id . What diff ere nce will th i s make to t he pH? Ka for
et ha no i c ac i d is 1 .7 X 10- 5 mo l dm - 3 •

Exe r c ise 80
A buf f e r s o l ut i on i s ma de up by mlx l ng 500 cm3 of 1 . 5 M etha noic ac id a nd
1000 cm3 of 0 .50 M sod ium et ha noa t e . 150 cm3 of this solut ion a r e t a ke n
and placed i n a bea ker conta ini ng 50 cm3 0 .10 M so di um hydroxide . How much
di ffe r e nce does t his ma ke to t he pH of th e origina l bu ffe r s o l ut i o n ?
Ka f or e t ha noi c acid i s 1 . 7 X 10 - 5 mo l dm- 3 •

87
Exercise 81
A buf fer solu t io n i s made by dis s ol vi ng sodium propanoate and pr opa noi c acid
in wa te r s o t hat t he c o nce nt r a t i o n of pr opano at e ion i s 0. 50 mol dm- 3 and
that of pro panoi c a cid i s 1 .25 mol dm-3 . Giv en that Ka for propanoi c acid
is 1 . 3 x 10- 5 mo l dm- 3, ca l c ul ate t he pH of :
(a ) the unc o nt a min at ed s ol ution ,
(b) a mi xture of 10 cm3 of the buf f e r s ol ut io n a nd 5 . 0 c m3 of 0 .10 M
hydroch l ori c a cid ,
(c l a mixt ure of 10 c m3 of the bUffer solu tion a nd 1 .0 c m3 of 1 .0 M
sodium hydr ox id e .

G - Calc ulating the composition of buffer solut ions

Exe rc i se 82
A bu ffer so lutio n of pH 4 .0 is t o be made fr om 1 .0 M propa noic ac id and
1 .0 M s od i um propanoate . What vo l ume of ea c h so l ut i o n mu st be mi xed t o give
100 c m3 o f the buf f e r solution required ? pK for prop a noic a cid is 4 .9 .
a

Exerci se 83
A buffe r s olution wi th a pH of 11.8 i s ne e d ed . 0 . 50 M s o l ut i o ns of di sodium
hyd rogen phosp ha te (V l , Na z HP0 4 , a nd s odium phosp ha t e (V), Na 3P04 ' are
a vai lable . pK for the HP0 4Z - io n is 12 . 4 .
a
HP0 4 Z -(aq) ~ P0 4 3 - ( aq) + H+(a q )
Wh a t vo lu me s of ea c h of t he s o l ut i o ns wo ul d yo u hav e to mix to gether t o
ma ke 200 cm3 of a buff er s o lu t i o n of pH 11 .8 ?

Exe rc i s e 84
Wha t concentrat i on of ammo ni um chlori de s o l ut io n sho ul d be mixed wi th an
equa l volume of 0 .40 M ammonia s o l ut io n t o give a buffer s olu tion o f
pH 9 . 5? pK f or NH4 +(a q) is 9 .3 .
a

Exerci se 85
A buffer so lution havin g a pH of 4 .4 is needed . Methanoic ac i d , pKa = 3 . 8 ,
and sodium methanoate would be s ui t ab l e . I f 0 . 80 M met hanoi c a c i d is us ed ,
what s hou l d th e conce nt rat ion of s od ium met ha noa t e be?

88
APPENDIX TWO
Calculat ing the pH of salt solutions

Objectiv e . When you have finished this sectio n, yo u should be able to :

( 41) cal culate the pH of a solution of a salt derived from either a
weak a cid or a weak ba se .

Whe n an aqueou s solu tion is made from a salt whi c h c o nt a i ns e i t he r an anion

from a weak acid or a cation f r om a weak base , an equilibrium is established
for whi c h there is an equilibrium cons t an t , called the hy dr o lys i s constant,
K . We now d erive this f or yo u .
h

Conside r a ny wea k a cid, HA , whi c h has an acid ioni za tion c o ns t a nt , Ka , and

it s so di um sal t , Na+A- . Whe n Na+A-(s) i s dissol ve d in wat er, this equili-
brium i s e s t a bl i s hed .
A- (aq) + H2 0 ( I ) ? HA ( a q ) + OH- (aq )
We can wr i t e an equilibrium cons t a nt , K
h
K = [HA( aq )] [OH- ( aq ) ]
h [A ( aq ) ]
By mu ltiplying the right -hand side by [H +(aq) ]/[H+(aq) ] we a re mult i plying
by uni ty and do no t c ha nge th e equa tio n :
K = [HA(aq)] [OH-( aq l] x [W ( aq)]
h [ A ( a q )] [W(aq ) ]
By gro up ing th e ri g ht - han d s i de di ff er entl y , we ca n s e e an ot her r elati onshi p :
_ [ HA ( a q ) ] + ._
Kh - [W(aq)] [A (a q)] x [ H ( aq ) J [OH f eq ) ]

But [H +( eq l ]. [OH - (aq) ] -_ K an d [W(aq)]

[HA (aq )]
[ A (aql]
1
w Ka
K Note t hat Kh i s th e same as the base
w
dis so cia tion co ns t a nt , K , f or A- (s e e page 69) .
Ka b
Howe ver, Kb va l ue s are rar e l y li st ed i n data boo ks .
So , yo u ca n cal c ul ate t he eq uil i br i um co ns t a nt fo r hyd r o l ys i s from Kw a nd Ka
fo r the ac i d fr om whic h the sa lt was de r iv ed .
Simi l a r ly , if th e sa l t i s d e r i ved from a weak ba s e, th e hydrol ysi s co ns t a nt
i s giv e n by :

He r e , Kh i s th e same as the ac id dissociation

c onsta nt , K a , f o r HA .

Kb i s th e dis so cia tion co nsta nt of a weak bas e, derive d in muc h the same way
as Ka • For in s tanc e , a mmoni a is a weak ba se whic h ac ce pts prot on s f rom
wa t e r t o form t he conjugate a c id, NH4 +, and hydro xide ions :
NH3 (a q ) + H2 0 ( I ) ? NH4 +( a q ) + OH-
The eq ui l i br i um c on stan t , Xc ' for th i s r ea ctio n is given by t he e xpression :
[N H4 +(aq) ] [ OH- ( a q ) ]
K
c [NH3(aq)] [H 2 0 ( l ) ]

89
Comb i ni ng t he two con stant s , Kc a nd [ H20 ( 1)J , into on e , we obta in :
K = [NH4 +(a q)] [OH-(aq)]
b [NH3 ( a q)]

In t he f o l low i ng Wor ked Exa mpl e , we show yo u how to use t hes e ex pr es s i o ns

to c a lc ul a t e t h e pH of s a l t s o l ut io ns .

Wo rk ed Exa mpl e Calc ula te the pH of a 0 .1 0 M s o l uti on of sodi um

et ha noate , CH 3 C0 2 - Na+(a q) .
K ( CH 3C0 2 H) = 1 . 7 X 10 - 5 mol dm- 3
a
Sol ut ion
1. Ca l c ula t e th e hydro l y si s c on s t a nt for t he r eact ion :

1 . 0 X 1 0 - ~ 4 mo 1 2 dm- 6 - 5 9 x 10 - ~ o mo l dm- 3
1 . 7 x 10 5 mo l dm 3 - •

2. Rewrit e t he e qu a t ion leav i ng s pa c e ab o ve and be low f o r i niti a l a nd

equ i l ib r i um concent rat ions . Fil l in the i nitia l co ncent rat io ns
a nd l et th e e q uil ibrium conc ent r a t i on of hy d r o xi de io ns be x mo l dm- 3 •

I nit i a l
0 . 10 0 0
c o nc n/mo l dm- 3
CH 3 CO2 - ( e q I + H2O ( 1 ) ;= CH3 C0 2H (aq ) + OH- (aq )
Equi l i bri um
0 . 10-x x x
c o nc n / mo l dm- 3
3. Write an express i o n f o r th e hyd rol ys is c ons ta nt i n t erms of co nc e ntrat i on :
_ [CH3 C0 2 H(aq )] [OH-( aq) ]
Kh - [C H3 C0 2 (aq )]
4. Sub st it ute the va l ue s :
(x mol dm- 3 ) (x mo l dm- 3 )
5 .9 x 1 0 - ~o mo l dm- 3
( 0 . 10 - x) mo1 dm 3
5. As s um e t hat (0 . 10 -x ) '" 0 . 10

x = I 5 . 9 x 10 - ~ ~ 7 . 7 x 10 - 6

[ 0 H- ( a q ) ] = 7 . 7 x 10 - 6 rno 1 dm- 3
6. As be f o re , c alc u l a t e [ H+( a q ) j f r om [ OH- ( aq) ] an d pH from [ H+( aq ) ] :
K
[W ( a q )] = [OH 1a q) ] 1 .0 x
7 . 7 x 10
1 0-~ 4
6
mo 1 2 dm - 6
mol dm 3
pH = - l o g [ H+(aq ) ] = - l o g ( 1 .3 x 10- 9 ) = ~

Now tr y some s i mi l a r pro b lems yo urse l f .

Exe r ci s e 8 6 Calcu l a te t he pH of the fol l owi ng so l ut io ns :

( a) 0 .010 M KCN ,
( b) 1 .0 M NH4 Cl ,
(c) 0 . 0 20 M NaF.
( Ans wers on page 108

90
 ( Ans we rs t o que sti ons f r om exami na t i on paper s a re
ANSWERS provi ded by I LPAC a nd not by t he Exami na t i on Boa r ds .)
Exe r c i s e 6
(a l NH, (aql + H' ( aq l .. NH . ' (aql + HaO( I )
Exercise 1
[ b) HaCO.(aq ) .. HCO, - ( a q ) + H' ( aq )
(a ) H
X o ( c] Ba (OH ) a ( s ) + 2H' (aq) .. Baa ' [a q ) + 2HaO[ 1 I
H+ 0 0
+ ~
0 0

o X
° Exe r c i s e 7
H
(a) HNo.( aq l + HaO( ) ) .. H, "I aq I
° + NO , - ( aq )
( b)
r<:J
Pyramidal . Of t he f o ur e l ectron pai rs r ou nd th e c en t ral ato m, on e i s ( bl HCOa H( a q l + HaO( ) ) .. H, o ' ( aq ) + HCOa-( a q)
non-bonded a nd will th ere f or e r ep el t he ot hers more s t r ongl y, j u s t a s
[c ) H. SO. ( aq J + HaO[ ) 1 .. H,o ' (a q ) + HSO . -(aq )
in the ammo ni a mole cule .

Exe r c i s e 2 Exercise 8
(a ) 3 (b) 2 ( c) 1 (a ) OH- (a q ) + H'( a q ) . Hao ( ) )
( b) HSo, - ( a q ) + H" ( a q) HaSo, ( a q )
Exercise 3 (c J HaD( I ) + H' [ aq ) H, O' ( a q)
(a ) OH-( aq) + H, O'( a ql [d) CO, a- [ aq) + H+(a q ) HCD , - [ aq)
. ...
.. 2HaO(I )
<D (b) CO,a - (aq l + H,O '(aq) HCO , - ( aq l + HaO( I I (e) HCO,-( a q) + H+ (a q) HaCO. ( a q )
....... . .
( d) SO. a - (aq ) + H, O'( aq ) . HSO . -(a q) + Ha0(l )

Exe r c i s e 9
Exerci s e 4 ( al HCO a H[aq) . H'[aq) + HCO a- [aq)
An a cid is a proton donor . ( b) Hao( I) .. H'[aq ) + OH -[a q)
.
A base i s a p r-ot.c n a c ceptor . (c ) HCo. - [ aq) .. H" ( a q ) + CO, a- (aq)
( d) HaS( a q ) .. H'[ a q ) + HS -(aqJ
(e ) HSo, - ( e q ) ... H' (aq ) + SO, a- (aq )
Exercise 5
(a ) NH , + HaD .. NH. ' + OH-
base 1 a c id 2 fle id 1 ba se 2 Exe r c i s e 10
( 0) HNO, + OW .. NO, - + HaD [a ) HaD and HCO. -
acid 1 base 2 biHJH 1 acid 2 (b) An a cid is a ny s ub s t an ce which i s abi e to giv e up a pr oton i n
(c ) HaD + HaD .. H,O ' + OH- solut ion to a bas e . When the au i d ha s lo s t ~ pro t on , i t fo r ms i ts
con jugat e ba s e .
bas e 1 a c id Z ac i d 1 base 2
il -
A bas e i s any su bs t a nc e whicn is ob l e to ~CC 8 p t a pr o t on in s o l ut i on ,
(d ) HSO, - + HaD . 50 3 + H,O ' f ro m a n ac i d . When t he ne s e no s uc cHpt ed d pr o t on . it forms it s
acid 1 base 2 base 1 od d 2 conj uga te ac i d .
 Exercis e 11 Exerc i se 15
( a ) , (c ] and (d) a re amphipro tic ·( a ) In 0 .0 10 M HCI , [H+(aq)) • 0 . 010 mo l dm- '
as a base as a n a ci d K • [H+(aq )] [ oH- ( aq )]
w
(a ) HS-( a q] + H+(a q ] '" HaS( aq ) HS- (a q ) '" H+(aq ] + Sa-(aq )
K 1 .0 x 10- 1• mol· dm- o
( c) Hapo.- (aq) + H+[aq ) '" H. po. [aq) Hap o.-(aq) '" H+(a q) + Hpo. 2 - (aq) = 11.0 X 10- 12 mol dm- ' I
: . [oH-(aq) ] = [W (~qJ] = 0 . 0 10 mo l dm- '
(d ) HC2o. -(aq) + W [aq ) '" HaCao .[aq] HC ao . - ( aq ) '" H+( a q ) + Cao.a - ( aq)
(b) In 0.1 0 M H, So., [W[ a q)] = 2 x 0.10 mo l dm- ' = 0 . 20 mol dm- '
(HNo. ca n a lso accept proton s , but only in the presence of an even stronge r
K = [W( a q ) ] [ o H- ( a q ] ]
acid tha n i t s el f, e. g. sulphu ric ac id: w
HaSo.(l) + HNo .( l) '" HaNo . +( l ) + HSo.-(l) K 1 .0 x 10- 14 mo I' dm-· = 15.0 X 10- 1 • mo l dm- ' I
We disc uss thi s rea ction f ur t her i n Uni t 01 ( Hydroca rbons ) , when we dea l : . [ oH- (aq] J = [W(~qJ] = 0.20 mo l dm-'
with the nitra tio n of benzene. ]
Exercise 16
Exerc i se 12 (a ) I n 0.0 10 M KoH, [ o H- (a q )] = 0 .0 10 mo l dm-'
(a ) (i ) HNo a [ii ] HCo. - (iii ) CH.Co .H ( av ) HCl K = [ W[ a q ) ] [o H-(aqJ]
w
[b ) In a mixtur e of pure nitric a c i d a nd c hl or ic (VI I ) a c i d , HClo. act s as an K
1.0 X 10- 14 mol a drn"
ac id , donating a proton t o HNo . and f orming i ts conjuga t e base , Clo. - . : . [W (aq] ] = [OH-1aq ] J = =1 1. 0 x 1o- 1a mol dm- ' !
0. 010 mo l dm- '
HNo . ac ts as a base , a cc e pt i ng a proton to form it s conjuga t e a c id , (b] I n 0 .050 M Sa( oH]. , [ oH-[a q ] ] = 2 x 0 . 050 mo l dm- ' = 0 . 10 mol dm-'
HaND . ' :
K
1 . 0 X 10- 1 • mol· dm- o
HNO. + HClo. '" Ha ND. ' + ClO. - :. [ W(aql] = [ oH- (: q J] = =1 1. 0 x 10- 13 mol dm- 'I
0 . 10 mol dm- '
<0
I\)
Exerci s e 13 Exer ci s e 17
Very f ar t o t he l eft, i. e . most wa t er mo l ecules a re un- ioni z ed . The hyd rog en ion concen tra t ion is grea ter i n pure wa t e r a t 40 ° C t han at
25 °C . Si nc e the ioniza tio n of wate r is a n e ndothermi c process , the va l ue
of Kw increases with i ncreasing t emp era t ur e, a s a shif t to t he ri g ht t e nds to
oppose t he effect of t he tem peratu re ch ange on the equi l i br i um by abso rbi ng
Exerc ise 14 energy . Mo re wa t er molec ules tend to dissociate a nd so the concentrat ion of
H.o( l) '" H+(aq) + oH-( a q ) hydr ogen i ons at a highe r tempera ture is greater .
K = [ H+(a q )] [o H-[ aq) ]
c [ Hao ( l)] Exercis e 18
- 16 1 d -. = [W ( aq ] ] [oH- (a q)] A: pH = 3 B: pH = 6 C: pH = 9
1 . 80 x 10 mo m 55. 6 mol dm- '
[W(a q ) ] [ oH- (a q ]] = 1 . 80 X 10- 16 mol dm-' x 55 .6 mo l dm- '
Exe r c i se 19
= 1 .0 0 x 10-1• mol ' dm-·
[W (aq) j = 10 mol drn"? = 1 .0 x 10 1 mo l dm-'
From th e equat ion , 1 mol of oH- a nd 1 mo l of H+ i s produc ed f or every mol e
of H,o ionized. pH = -l og [ W ( a q ) ] = - l og ( 1 x 10 1) = -(0 + 1] =8]

[H+[aq)] = [ oH-(aqJ ] = 1 1.00 X 10- 1 • mol· dm-· = 1 . 00 x 10- 7 mo l dm- '

The fra c tion ionized is g i ve n by : Exercise 20
a mou nt ion ized = 1 .0 0 x 10- 7 mol K 1 .0 ~ 10- 1 • mo l a dm- o
= 1 1 . 80 x 10-' 1 w = 1. 0 X 10- 1 • mo l dm- '
i nitia l amount 55. 6 mo l [ W ( aq J J = [OH-( aqJ] = 10 mo l dm- 3
( ap pr oximately 18 mol ecu les i o ni z ed i n 10 000 000 000 ) pH = -log[ W( aq ]] = - l og (1. 0 x 10-10 ] = o - (-15] = @]
 Exe r c l s 8 2 1
Exercise 26
fa ) K = [H' l aq ) j [o t-n a q ) ]
w (a ) pH = <Log (H'(aq)] = 9 . 0
, _ Kw _ 1 . 0 X 10- 10 mo l · d m- 6 _ - 6 _.
[H Leq l ] - [ OH ( aq ) ] - 1 . 0 x 10 - . mol dm- ' - 1 , 0 x 10 mo l dm l o g [ W[ a q )] = - 9 . 0
6 : . ( 11'( eq l ] = a nt ilog ( -9,0 ) = 11. 0 x 10 - ' mol dm-'I
pH = - l og lH' ( a q J j = - l og ( 1. 0 x 10- ) = 0 - ( - 6 . 0) = ~
(b ) pH = - To g [W(aq l] = 2 .0
I b) K 6
1 .0 x 10- " mol · dm- 1
. 1 .0 X 10 - • mol dm- ' log [H'(aq) ] = -2 .0
[ H' ( a q ) ] = [ o H-1aq lf = 0 .10 mol dm- '
pH - - l o g [ H' (aq) ] = -log ( 1 . 0 x 10- 1» = 0 - ( - 13 . 0 ) = ~ : . [H' (aq)] = a ntil og (-2 .0 ) = 11 . 0 x 10 - · mo l dm- 3 !
(c I K
1, 0 X 10- 1 " mol · dm- 6 10
[ H'( a q l ] = l OH-1aq1] = 1 .0 X 10- 4 001 dm 3 = 1 . 0 X 10 - mol dm- '
Exe r cis e 2 7
pH : -l o g [ H' (aq ) ) = -L c g ( 1 . 0 x 10- 1 ° ) = o - [ - 10 . 0 ) =~
p H = - Log [H'[aq)] = 9 . 20
lo g [ W t eq l ] = -9 .2 0
Exe rc f s e 2 2 1 0
., [H'(aq)] = antilog ( - 10 + 0 .80 ) = 16 . 3 x 10 - mo l dm- 3 1
pH = - l o g [ H' ( a q ) ]
= -l o g ( 7 . 0 x 10 - 7 ) = - [ -7 + 0 .04 51 ) = - [- 6 . 154 9 ) = §]
Exe r c i s e 26
pH • - l og [ H' ( a q ) ] = 2 . 6 3 2
CD
W Exe r c i s 8 23 l og [H ' ( aq ) ) = - 2. 63 2
pH = <Lo g [H'[ aq ]] = - Lo g [ 3 . 2 x lO- 'J = - (-9 + 0 .5052 ) = - [-8 .4 948) = §J 3
:. [H ' [ a q)] = antilog [ - 3 t 0 .3 6 8) = 12 . 33 x 10 - mol dm- J I

Exe r ci s e 24 Exe r c is e 29
K = [H' (a q ) ] [ o W( aq)] [a) 1
w [ W [ a q)] = 0 . 10 mol dm- 3 = 1 .0 x 10 - 00 1 dm- '
I n pu r e wat er, [ W (aq J] = [ OH-(aq ) ] so t ha t K = ( W (a q) ] · pH = - l og [ H' [ a q ) ]
w
.. l H' ( aq ) ] = / 0 . 30 x 10 10 moI 2 dm- 6 0 = -L o g (1. 0 x 10- 1 ) e - [ - 1. 0 ) = ~
= 5 . 48 x 1ll- mo 1 dm- 3
0 (b) (H '[a q ) ] = 0 .0 1 mol dm- ' = 1.0 X 10 - 2 mol dm- 3
pH = - l og [ W [ a q ) ) = - l o g (5 . 40 x 10- ) = - (-8 t 0 . 7386 ) = - ( - 7 , 26 12 ) = ~
p H = - l og [H' [ aq) ]
= - l o g [1 x 10. 2 ) = - [ -2.0) = ~
Exerci s e 25
[c ) [ W [ a q )) = 1. 0 x 10-' mol dm- 3
K = [ H' (aq )] ( o W[ a q )]
w
pH = -l o g [ H'[ aq))
I n pure water [ H' ( aq l] = [ OW (aq l ] s o t ha t K = [H' (aq) J2
w
= -l o g [ 1 x 10 - 3 ) = - [ - 3 .0 ) = ~
5 . 4 7 X 10- 10 mo1· dm- 6 = ( H' t e c ) J.
(d ) ( W( a q ) ] = 1 . 0 x 10 - " mol dm- 3
10 7
[H' [aq) ] = /5 . 47 X 10 - mol· dm- 6 = 2 . 34 x 10 - mo l dm- '
pH = - log [H'[ aq) ]
7
pH = - l og [H' (aql ] = - l o g (2 . 34 x 10- ) = - [ -7 + 0 . 369 2) = - ( - 6 . 6308 ) = ~
= - l o g ( 1 x 10 :: " ) = - [-4 ,0 ) = ~
 Expe r i ment 1 Speci men r e s ul t s Exper i me nt 2 ~ec i men r esult s
Result s Ta bl e
Resu l t s Ta ble 2
Concentration of Obser ved pH of so l uti on s Cal c ula t e d pH of so l uti o ns
ac id molldm- ' of e t ha no i c ac i d of hydro chloric acid Concent ration
Aci d /mo l dm- ' pH
0 .0 0010 4 .2 4 .0
Bor i c a c id 0 . 01 0 5 .6
0 .00 10 3.5 3 .0
Be nzo i c ac id 0 .0 10 2.8
0 . 0 10 3.0 2 .0
EU,a no i c acid 0 .0 10 3 .0
0 . 10 2 .7 1 .0
Uin yJ ro g e nphos phat e (V I i o n 0 . 01 0 4 .6
Expe riment Que s tions
1. [a ) In ea ch c a s e , the hydro chlori c a ci d so l uti on ha s a high er co nce n-
trati on of hyd ro gen io ns tha n th e etha noi c a ci d s o l ut i o n of the
Exerc ise 30
s a me co nce nt r a t i o n .
( b) Thi s s hows t ha t t he e t ha noic a c id so l ut i on s are in compl e t el y Ta bl e 2
d i s s ocia t e d .
Aci d Equil ibr ium in aqueou s so l ut i o n Ka /mol dm-'
2. ( a) As t he et ha no i c a c id is dil uted , i t s pH be comes cl os e r and c l os er
Et ha no ic ac id CHaC0 2H(a q) ~ H'( aq) + CH.C0 2-( a q ) 1 .7 x 10- '
to th e pH of the s t ro ng ac id at the s ame c once nt r at i o n . Thi s s hows
that di l uti o n in c r ea s e s t he ex te nt of di s s oci at i on of et ha noi c a c id . Benzoic ac i d C.H ,C 0 2H( a q) ~ H'[ a q ) +
C. H, C0 2-( aq ) 6.3 x 10- '
The s a me is true of o t he r weak acids .
Ca r bo nic a cid H2CO.( aq) ... H'(a q) + HCO. -Caq) 4 .5 X 10- 1
The t rend i s cont i nued at g r ea t e r di lution , but pr ecise meas ur eme nt
Nitro us aci d HN0 2 ( aq ) H' Leq l + N02-( a q ) 4 . 7 x 10 - -
becomes much rrore diff i cu lt due to co nta mi na t i o n of t he s a mpl e wi t h ..
dis sol ved CO 2 , Boric acid H.B Oa( a q) .. H'(aq ) + H2Bo . -( aq ) 5 .8 x 10- 1 0
Howev er, calcu l at io ns sh ow t hat even at a con centration of Hydroge nsu l phite ion HSO a - Ca q ) . H'Ca q) + So . 2-C a q) 6 . 2 x 10 - 9 '
<.0 10- 6 mo l d m- ' , the etha noi c a cid wo ul d not be quite ful l y d i ssoc i -
~
a ted ; i t woul d ha ve a pH of 6 . 02 as compa r ed with pH of 6 .00 fo r a
s t rong a c id . (b) Or der of ac id st r en gth. st ro ngest f i r s t :
( b) The ful l e qua t i on for the d i ssoc i at i o n of et ha noi c acid i n wa t e r i s : ni t r o us a ci d > benzoi c a ci d > et ha no i c aci d > ca r boni c aci d >
CH. C0 2 H( a q ) + H2 0 ( I) ~ CH.C 0 2-C a q ) + H. O· Caq ) hyd r oge ns ul ph i t e i on > bo ric acid

The add i t io n of wat e r decr eases t he con c e nt r at io ns o f e t ha no i c ac i d ,

etha noa te i ons a nd hy d r-o ge n ion s . Bec a use t wo o f t hes e ar e o n t he Exe r c ise 31
r i gh t of t he eq uat i on a nd o nly o ne on th e l eft , a s hi f t t o t he ri ght
goe s f urt her t owa rds r e st o r in g t ne o r ig ina l co nce nt r a t io ns t ha n a Fi r st , ca l c ul a t e [ H' Caql ] fr om pH
s hi f t t o t he l ef i . The dec r ea s e i n co nce nt r a t i o n r e d uc e s t he r at e
pH - <Lo g [H'(aq ) ] - 4 . 17
of reac tio n R - L t o a g rea te r e xte nt t han L - R. Thu s . t he acid
be c omes i nc r ea s i ngl y d i s s oci at ed on d i l ut i on . l og [ H' Caq) ] - - 4 .1 7
Note t ha t t he al t e rn ati ve s i mpl e r a r g umen t . t hat th e add ed wa te r : . [ H' ( a q )] = antil og -4. 17 = an tilog C-5 + 0. 83) = 6 . 76 x 10-' mol dm- '
i s pa r t i a l l y used up in a s hift to t he r i g ht , i s i nva l i d b e ca us e At eq uil i brium . t he co nc e nt r a t i ons of hyd r og e n i on a nd hyd r ogenc a r bo na t e i on
th e co nce nt r a t i o n o f ~ r e main s e f fe c t i ve l y c onst a nt . are th e sa me ( 6 . 76 x 10- 5 mol dm-')
I niti a l
concn / mo l dm- ' 0 .0 10 o o
Ex peri ment 2 Ques ti o n H2 CO3 ( a q ) ~ H' ( aq) HCO . - ( a q )
Orde r of ac i d s tren gth , s t ronge st ac i d f i r st : Equil i br i um
( 0 . 0 10 - 6.76 x 10-' ) 6 .76 X 10- 5 6 . 76 x 10- 5
co nc n/ mo l drn- '
be nzoic ac i d> et hanoic acid> di hydrog enphosp ha t eCV) i on> boric a c id
(6 .7 6 x 10-' mo l dm- ') 2
Ka = = (O . UlO - 6 .713)(- 10- " mol dm 3)

Si nce the n 0 .0 10 - 6 . 76 x 10- ' ~ 0 . 0 10

x 10 -' mol dm- ' )2 = 10- 1 1 d -'1
Ka _ (6 .7(06 . 01 0 mol dm- ' )
14 . 57 x mo m
( 4 . 60 x 10- 1 mol dm- ' with out appro xima t i on . )
 Exe r c is e 32 Exer cis e 34
First , ca l c ul a t e [ H' ( a q ) 1 fr om pH I nit i al
e o ne n/mol dm- ' 0 .1 00 o o
pH " -log [ H'(aq ) ] " 3 .28
HID. (aq ) .. H' Leq ) + ID. - (aq )
l og [ H' ( a q ) ] " - 3 , 28 Eq u i l Lb r-i urn
eo ne n/ mol dm- ' ( 0 , 100 - x ) x x
: . [ W ( a q ) I = antilog ( - 3 .28 ) " a n t il o g (-4 + 0 .72) " 5 . 25 x 10- ' mol dm- 3
K "[W (aq l] [ID.- ( aq l ]
At equi l i br i um. t he co ncent r a t i on of hydr o gen ion i s e qual t o t he co nc e nt r a -
a [ HID. ( a q ) ]
t io n of be nzoat e io n , i . e . [c. HO e0 2 -l a q ) ] • 5 , 25 x 10- ' mol dm- 3
0 .1 7 mol dm-' x 2 mol 2 dm- '
I nit i al
0 . 005 0 o o (0 . 1lfo~XJ mol dm-=
co nc n/mol dm- '
C.H o e 0 2 H(aq ) ~ W ( aq ) + Co 0 .100 • 0 . 588 < 1000
e. Ho e0 2 " I aq ) In thi s ca s e, K
Equil i br ium a 0 .17
e one n/mol dm- ' (0 .0 050 - 5 .25 x 10- 0 ) 5 .25 x 10- 0 5 .25 x 10 - 0
The r ef or e x cranno t be i gno r ed i n t he bo t t om li ne and a q uadratic equ atio n
[ W ( aq ) ] [ C.HO C02 -( aq) ]
K mus t be so lv ed , The e xpr es s i o n be come s :
a [ C. HO C0 2 H( aq ) )
(5 .25 x 10- 0 mo l dm- 3 ) ( 5 . 25 x 10- 0 mo l dm- ')
x2 Or x2 + 0 . 17x - 0 . 0 17 o
1 6 , 16 x 10 - 5 mol dm '1 0 .17 ~ ( 0 . 100 - x )
( 0 .0044 75 mo l dm- 3 )
- 0 .1 7 :!: r ( 0 .17) 2 - 4 ( 1 x - 0 . 017)
Exe r c ise 33
x =
2
(a )
K 1 2
w 1.00 x1o- • mo 1 dm- · , 2 . 00 x 10- 1 • mol dm- ' - 0 .1 7 + 0 .3 11
[ W ( aq ) ] [ o H-( eq l ] 0 . 070 5 or -0 , 241 (ab su rd roo t ! )
0 .0 500 mol dm 3 2
1
pH = - l og [W( eq l ] - l og 12 . 00 x 10- . ) - (0 .3 010 - 13 . 0000) " ~ [ H' ( a q )] • 7 .05 x 10- 2 mo l dm- '
( b) In it i al pH " - l og [ H+[ a q) ]
0 . 100 o o
CD eo nen /mo l dm- ' - l o g ( 7 . 05 x 10- 2 ) • - ( -2 + 0 , 84 8 ) • ~
(Jl CH. C02 Hlaq) ~ H+ l aq ) + CH. C0 2 -( aq )
Equi li bri um
eo ne n/mo l dm- ' 0 . 100 - x (I f yo u had wr o ng l y i gno r ed x o n the bo t t om l i ne you would ha ve ob tai ned a
x x
va l ue of pH • 0 . 886 . )
[ H' l aq ) ] [ CH. C0 2 - ( aq) ]
K
a [CH.C 0 2 HI aq ) ]
Experiment 3 Spec ime n re s ults
1 . 69 x 10- 0 mo l dm- ' ~ Ix mo l dm- ') ( x mo l dm- ' l
(0 . 100 x l mol dm- 3 Res ult s Ta bl e 3

Assumi ng t ha t x « 0 . 100 , (Co " 0 , 100 > 10 00 ) p H o n add i t i on of pH o n a dd i t i on of

Ka 1. 69 x 10 0 . 1 M Na oH to 0. 1 M HCl t o
( 0. 10 0 - xl 0 . 100 Volume
0 x2 add ed buf f er pur e wa t e r bU f f e r pure wa t er
1 .69 x 10 -
0 . 100
0 7 .0 6 .9 7 .0 6 .B
x " I 1 .6 9 X 10-· 1 . 30 X 10 - ' dro p 7,0 9 .8 7,0 4,1
[H '( aq ) ] " 1 .30 X 10- ' mo l dm- ' 1. 0 e m' 7.1 10 . 5 6 .9 2.7
pH " - l og [ W I e q ) ] " - l og ( 1 . 30 x 10-') - I 0 . 1139 - 3 . 0000 ) 5. 0 e m' 10 . 0 11. 6 6 .0
~ 2.1

pH of pur e wat er wi th
6 ,9
mi ni mum ai r e xpos ure

pH of pu r e wa te r aft e r I
5.4
10 mins a i r expos ur e
 Expe r iment 3 Que s ti o ns Exerc ise 37
1. You wi l l pr obabl y r e cor d a ch an ge of ab out 4 p H uni t s . Theore t ic a l l y , (a ) Init ial
co nc n/mo l dm- ' 0 . 100 o o
t he ch an ge sh ou ld b e fro m pH 7 . 0 t o pH 2 . 4 so , if e ver yt hing is right
i n you r e xperi ment, you mi ght en swe r 5 pH uni ts . CH. CH.CO.H( e q l CH,CH. CO. -(a q ) + H' ( aq)
Equilibrium
2. Assu ming t ha t the pH of pure wa t er aft e r the add it io n of ac i d wa s 3 . 0 , ( 0 . 100 - x ) x x
concn /mo l dm- '
to the n ea r es t uni t,
[ W ( a q)) = 1 .0 x 10- ' mol dm"':· K
a
i n pure wa t e r (pH 7 . 0) • 1 . 0 X 10- 7 mo l dm- J
1. 3 x 10-' x·
( ca nc e lli ng uni t s l
a cid = 1 .0 x 10-' mo l dm-·. 10' (0. 100 - x l
'>';";-'-ri";7+-'::';'-;-=;i;-n:=-'p:':u:':r:"e=w:'a'-:t:"
:' e'"'r=-==:'=' 1 •0 x 10- 7 mo 1 dm -3
00 0 .100 > 1000
I n othe r wor ds , a decrea se of 4 pH units means the r e a re 10' Ka 1 .3 x 1O- :s 0 .100 - x 0 .1 00
[or 10 , 000 ) t i me s as ma ny hydr ogen ions in th e same vo lume .
x' 0 . 100 x 1 .3 x 10-'
3. Almost a l l the hydro gen i on s mu st have rea c t ed wi th the buffer s o l uti on.
You wi ll f i nd o ut what this rea ct i on i s i n the nex t se c tion .
x 1 1. 3 x 10- 0 1. 1 X 10-'
4. Carbon di ox id e i s a bsorbed fr om the ai r a nd re a cts with wa t e r to f o rm
hydrogen i ons . [H' ( e q l ] = 11 . 1 x 10- ' mo l dm- ' !
CO .(aq) + H. O(l ) "" W(aq) + HCO. - ( a q ) (bl In it ia l
co nc n/mo l dm-' 0 . 100 0.05 0 o
The di st i lled water you norma l l y us e in t he laboratory i s pur e e no ugh ~
CH. CH.CO.H ( aq) CH.C H. CO. - (aq ) + H' ( a q)
for most pur pos e s , but neverth eless i t r apid l y becomes somewhat 1: c i di c . Equ 11 ibrium
( 0 . 100 - x ) (0 . 050 + x) x
conc n/mol dm-'

K
co Exer cis e 35 a
(j)
A buff e r s o l ut i o n is one th a t can r e s i s t c ha nges in pH when a c i d or a l ka l i 1 . 3 x 10-' x
( ca nce l li ng uni t s I
i s ad ded to it .
0 _ 0 . 050
- 1 .3 x 10-' > 1000
°K
a
Exerc is e 36 (0 . 0 50 + x) ~ 0 . 0 50 a nd ( 0 . 100 - x ) 0 .100
(a) Hydr ogen i on s fro m the c ont ami na t i ng acid rea ct wi th pro pa noate ions , . 050 x
s o that t he e qu i li br i um i n t he r ea c t ion 1 . 3 x 10 - ' = 0 0.1 00
CH.C H.CO. H[a q ) ~ CH. CH.C0 2 -( a q ) + H' [ aq) 1 . 3 x 10- 5 x 0 .1 00
x 2.6 X 10- 5
is s hi f t ed to th e left . Thi s r emo ve s mos t o f t he e xt r a hydro gen i o ns 0 . 0 50
from so lutio n a nd so the pH i s a l most unc ha nged .
[ H' (aq) j 1 2. 6 x 10- 5 mol dm- ' I
(b ) Hydro xi de i o ns f r om conta min a t i ng al kal i reac t with un - i o ni zed
propanoic a c i d mole cu l e s . a cc or di ng to the eq ua t i on :
OH- ( a q ) + CH. CH.CO.H p CH. CH. CO. - ( aq ) + H. O( l ) (c) Pro pa noic aci d s o lut io n has a great er hydrogen i on con ce ntrat i on t ha n
the buf f e r s o l ut i on co nt a i ni ng t he same c once ntratio n of propa noic a cid .
Thi s remo ves most of th e ad ded OH- io ns f r om the solutio n and pr ev e nt s I n o t he r word s, th e i on i zation o f t he wea k a c id i s s uppr e ss ed in the
a ny s i gn i f ic a nt chang e i n pH. buffer s o l ut io n . Thi s s ho uld not s ur pr i s e you , i f you a ppli e d
Le Chat el i er ' s princi pl e t o t he eqGi librium:
CH.C H. CO.H(aq ) '" CH.C H. CO. -(aq ) + H' ( aq)
An increa s e i n t he conc ent r at i o n of pro pa noate i o ns wi ll ca use t he
e qui l i br i um t o s hif t t 6 the l eft , i nc r eas i ng th o c o nc ent r a t i o n of
un -io nized a cid and dec r ea s i ng t he c once nt r a t io n o f hydro ge n i o ns .
Exe rc ise 38 Exerci se 39
Amount of a c i d in s olutio n 4 Sui t a ble i ndi cat ors t o c ompl e t e th e pat t e rn ar e sh own bel ow, but so me others
aV 0 . 090 mol dm- ' x 0 . 010 dm' = 9 . 0 x 10- mol
may als o be sui table .
Amo un t o f s a lt i n so l utio n aV 0 .15 mo l dm-' x 0 . 0 10 dm ' = 3 . 0 x 10-' mol
n 9 .0 x 10- 4 mo l
Con cn of a c id in buff e r 0 . 030 ~ = 0 . 0 30 mol dm-' indicator pH range
V
I I
3 . 0 x 10-' mo l
Co ncn o f s a l t in buf fe r =V 0 .1 0 mo l dm- ' alizarin yellow yellow red
0 .030 dm'
pH = - l og [W[a q) J = 5 . 85 phenolphthalein colourless re~
[ W [a q ) J = an til og ( - 5 . 8 5) 1. 41 X 10- 6 mol dm- '
phenol red yellow r red
I ni tial
0 .030 o 0 .10
concn/mo l dm- · litmus red blue
HA( aq J W [ aq) A-( eq l
Equilibrium methyl red red I
0 . 0 30 - 1 .4 1 X 10 - 6 1 . 41 x 10- 6 O. 10 + 1 .41 x 10- 6 II yeilow
co nc n/ mo 1 dm-'
[ W ( aq) J [ rr a q) ) bromophenol blue yellow I I bue
K
a [ HA[ aq) J
thymol blue red yellow
1 .4 1 X 10- 6 mol dm-' x [0 . 10 + 1. 41 x 10- 0 ) mol dm- '
[ 0 . 03 0 - 1 . 41 x 10 0) mol dm- J 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

6 pH
" 1. 4 1 X 10 - mo 1 dm- ' x 0 . 10 mo I dm-' = 6 I d -'I
0 .030 mo 1 dm .,
14 . 7 x 10- mo m

Exerc ise 40
[a ) Litmus ha s a wi de r pH range than o the r i ndi c ators. This means t ha t it
may not c ha nge co lo ur r a pi d l y enoug h t o give a pr ec ise indi ca tio n of
when a so l ut io n becomes neut ra l . [ If you are wonderi ng wha t us e i s an
indi ca t or whic h does not ch a nge co lo ur around pH 7, you wil l f i nd out
l a t e r in th e Unit . )
(b ) Br omot hymo l blue . pH r a nge 6 . o to 7 . 6 . o r perha ps phe nol r ed. pH ran ge
6 . 8 to 8 . 4 .

Exerc is e 41
2HCl(a q ) + Sa [OH). (aq ) BaCl . Leq ) + 2H. 0( 1 )
-
Amoun t of Ba( OH) . = 0 . 15 mol dm- ' x 0 .020 dm' = 0 .0030 mol
From t he eq ua ti on, amount of Hel = 2 x a mount of Ba (OH).
= 2 x 0 .0030 mol = 0 .0060 mo l

Volume of HCl = 0 . 0060 mol = 0 024 d '

o . 25 meI dm J • m = ~

The pH was meas ured in a buf fe r solu ti o n to en~u r 8 t h~ t t he pH did not c hange
t oo r a pi d l y o n the add it ion of a lka l i . I t would be a lmost impossi bl e to
Cha nge t he pH of t he solu tion in a c ont ro lled way without us i ng a buff e r .
 Exerc is e 42
Exerc i ofJ 43
(a ) Phe nolp ht ha lein ha s a pH ran ge of 8 -10 . It wou ld. t here fo re . r ema i n in I I (a ) Rod
i n i t s a c id f orm ( col our less) beyo nd t he equival e nce poi nt a t pH 5 .
The pi nK co lo ur wou l d no t appear t i l l a bo ut pH 8 whic h wou l d requi re an I I [ bJ pH = pK - l og
In
e xcess of ammon ia .
At t he beginning of t he colour c ha nge . [HIn (aq ) J/ [I n- ( aqJ ] = 10
( b) Me t hyl r ed . pKl n = 5 .1 . This i ndi ca to r woul d sho w a n i nt e rmediat e
co lo ur be t ween pH 4 .2 and pH 6 .3 which . of co u rs~ . i nc lud es pH 5. the pH = pK - 10g 1o = 5 .1 - 1 = 4 . 1
equi va l en ce poi nt . 1n
At the e nd of the c ol our chan ge , [Hln[aq J]/ [In -(aq)] 0. 1
At th i s st ag e. you cannot tel l whethe r the end- point wi l l be ' s ha r p'
( s ee page 48) . but you will lear n more fu l ly about t he c hoic e of .. pH = pK - l og 0 . 1 = 5 . 1 + 1 = 6 .1
In
indicators in t he sec t ion on pH curves later in t his Uni t .
pH ra nge =14 . 1 t o 6 . 1 I
(c ) 0 .0 10 M He l i s d i luted from 1 em' t o 500 cm~
Experi men t Specimen r es ult s
:. new concen tra t io n = 0. 0 10 mo l dm- ' x 1/ 500 = 2 . 0 x 10- ' mol dm- '
Method 1
[HI n( aq J ] 7 Since HCl i s compl e tely io niz ed , [H · : aq J ] [HCl ( a q J ]
Bes t colour mat ch wi t h t ubes cor respon din g to [ I n ( aq) j
3" 2 .0 x 10- ' mo l dm- '
pH = pK -l og [Hl n(a q ) ]
ln [ I n ( cq ) j pH = -log ( 2 . 0 x 1o- ' J - ( 0 . 30 - 5 ) =~
a q )] 7
pK = pH + lo g [[ IHln n([ aq)]
ln = 3 .7 + l og 3" = 3 . 7 + 0 . 37 = 4 .1 ( d) pH = pK
In
KIn = a nt il og ( -pKln J = an ti log ( - 4 .1) = 17 . 9 x 10- ' mo l dm- ' I va lue s ,
Method 2 4.7 = 5 . 1 -log
co Best co lour ma t ch when 3 . 0 em
co t ~I ~ ~aqJJ
n aq) J 1 . 6 em =
1. 9
lo g 5. 1 - 4.7 = 0 .4
pH = pK
-log [HIn ( aq )
In I n,- ( aq ) ] .. - = an t ilog (0 . 4 ) 2. 5
_ [HIn( aq) ] [ red ] _ _ ro4l
pKl n - pH + log [ I n-[ aq) ] = 3.7 + log 1.9 = 3.7 + 0 .28 = 4 .0
[ye ll ow] - - ~
KIn = an t il og ( -' pKI n ) = a ntilog (-4 .0 J = [1 . 0 x 10- ' mo l dm- ' I

Experiment 5 Que sti ons Exe rc i se 44

1. The wedge method gives a con tinuous r a nge of co lours , whi ch maKe s Ta bl e 4
compari so n ea s i e r , a nd a voi ds t he d i f f icu lty of l OOKi ng th roug h c ur ved
s ur fa c e s . Ho weve r , t he a ppara t us i s mo r e e xpe nsi ve a nd req Uires la rge r I nd i ca tor IpH range pH 1 pH 2 pH 4 pH 6 pH 8 pH 11
vol umes of s olu t i ons .
Thymo lp htha l ein 8 .3 - 10 .6 - - - - - b l ue
2. The to ta l con c en t ra ti ons of i ndicat o r , [Hln(aqJ J a nd [ I n- ( a q ) ] had t o
be the s a me i n the so l uti ons be i ng compa r ed , o t herw ise a ch a nge i n Methy l r ed 4.2 - 6 .3 red red r ed o ra ngs ye l low ye llow
densi t y might be c onf use d wit h a cha nge in co lour .
Me t hyl yellow 2 .9 - 4 .0 red r ed ye-ll ow ye llow ye l low ye ll ow
3. A buffe r of pH 8 co ul d not be us ed s i nce pH 8 i s out side th e pH ran ge
of th e i ndi ca t or . Col o ur compa r i so ns can on ly be made when t he r at io Br omo th ymol blue 6 .0 - 7 .6 yellow ye llow yellow ye llow blue bl ue
[ Hl n( a q ) J/ [ I n- ( aq ) ] i s betwee n 10 an d 0 . 1 [ap proximate ly) . Thymo 1 bl ue 1 .2 - 2 .8 red o ra nge ye l l ow y ello w yel low bl ue
8 .0 - 9 .6

' Uni ve r s a l ' I r ed I or ange- I or a nge I ye l l ow ye l low

red yel low
Ig ree n Igb lur eee-n
 Ex perime nt 6 Que st i on s
Experi me n t 6 S pec ime n r e sul ts
[All th e numer ica l an s wer s i n lhe ta~ le b e l ow assu me that th e a c id s and
alkal i~ were p rec is e l y 0 .1 00 M)
Re s u lts Ta b l e 5

0 .1 0 0 M NH, add ed t o 25 . 0 Col' of 0 . 100 M CH, COzH 0 . 10 M Cfl. CO, H 0 .1 0 M CH, CO, H 0 . 10 M HC l 0. 10 M HCI
0 . 10 M NH. 0 . 10 M INaO H 0 .10 M NH, 0 . 10 M NaO H
Vo lume/cOl " 0 .0 5 .0 10 .0 15 .0 20 . 0 24 . 0 24 . 2 2 4 .4 24 .6 24 . 8 24 .9
pH 3 .0 4.2 4.6 4 .9 5.3 Q1 NONE pH 7 .4 - 10 . 2 pH 3.6 - 6 .8 p H 3 .G - 10 .2
6.2 6.3 6 .4 6. 6 6. 7 6 .8
Volu me/cOl ' 24 . 9 5 25 . 0 2 5 .0 5 2 5. 1 25. 2 2 5 .4 25 .6 25 .8 26 .0 30 . 0 35 .0 (;)2 25 .0 em" 25.0 Col" 2 5 .0 Col ' 25 .0 Col'
pH 6 .S 7. 0 7 .1 7 .2 7 .3 7 .4 7 .6 7. 7 7. 8 8 .6 8.9
(;)3 0 , 0 .1, 0 0 , 2 .5 , 0 0 , 2 .5 , 0 0 , 6 .0 , 0
0 .100 M NaOH a d d e d to 25.0 Col' o f 0 .10 0 M CH3 COz H
P HENO LPHTHAL EIN MET HYL ORANGE
Volume/cOl ' 0.0 5 .0 10 . 0 15 . 0 20 .0 24 .0 24.2 24 .4 24 . 6 24. 8 24 . 9 t h ymol r ed bromop he nol b lue all men ti o n e d
in previou s
pH 3 .0 4.2 4. 6 4.9 5.3 6.2 6 .4 6 .6 6. 9 7 .2 7 .6 thymo l blue c ongo red
(;)4 NO NE: co l urnns , p l us
Volume/c Ol' 24 .95 25 .0 2 5 . 0 5 25 . 1 25 .2 25 .4 25. 6 25.8 26 .0 30 . 0 3 5. 0 thymo l p hthale in b r o moc resol green Ii t mus
pH 8. 1 9 .0 9 .5 10 .0 10 .6 10 . 9 1 1 .2 11 .3 11 . 4 1 ', . 9 12 .2 bromo t hymo l b l ue methyl r e d
p heno I r ed bromo creso l p ur p le
0 .100 M NH, ad d ed to 25. 0 Col' of 0 . 100 M HCI

Volum e/em' 0 .0 5.0 10 .0 15 . 0 20 .0 24 . 0 24 .2 24 .4 24 . 6 24 . 8 24 .9

pH 1. 0 1.2 1 .4 1.6 2 .0 2 .7 2.9 3.1 3 .3 3 .8 4 .6 Exercise 4 5
Vo l u me/em' 24 .95 2 5 . 0 2 5. 0 5 25 . 1 25. 2 25 .4 25 .6 25 . 8 2 6 .0 30 . 0 35 . 0 (a ) Phenolp hthalein become s co l o u r les s at 13 . 0 e m" of a dde d HCI.

co pH 5 .3 6 .0 6 .7 7 .1 7 .3 7 .5 7.6 7.7 7 .8 8 .6 8 .9 C11. 6 Col" i s a l so a c c ept a bl e since t he no r mal pr a c ti c e is t o t a ke t h e

co mi d - po i n t of th e p H range. Howeve r , p he nolpht ha l e i n is a spe c ia l case
0 .100 M Na OH added t o 2 5 . 0 C ol' o f 0 . 100 M HCI sin ce one of the fo rms ~ f t h e i ndi c a t or has no colou r at a l l . Th us,
the pink co l ou r c o u l d stil l be de tect e d (at d i f fe r e nt i nten sit i e s
Volume/cOl' 0 .0 5.0 10. 0 15 .0 20 .0 24. 0 24 .2 24.4 24 .6 24 .8 24 .9 t hro ug ho ut t he ra n ge .)
pH 1 .0 1 .2 1 .4 1.6 2 .0 2 .7 3 .0 3.5 4. 0 4.6 5 .0 Met h y l ora nge t ur ns r ed at 2 5 . 5 em' of added HCl .

Volume / em' 24 .9 5 25 . 0 25 .05 25.1 25 .2 25 .4 25 .6 25 .S 26 .0 3 0 .0 35 .0 [ b) W(aq ) + CO? - Ca q) .. HCO, - [ eq )

pH 5 .2 7 .0 8 .9 9.8 '10 .6 10.9 11 .2 11 . 3 11 . 4 11 . 9 12 .2 or H.O ·Caq ) + CO. ' - Caq) .. HCO ,, - Caq) + H,O Cll
[c ) Methy l ora nge . The curve is steepe r in th i s regi o n - t his means that
Spec ime n c urves , for refe re nce purposes , ar e on pa g e 110 . the c ompl e t e c o l o ur change occurs f o r a muc h s mall e r ad d i t i o n of ac id
- on l y ab o u t 0 .6 em" i n this case . CEve n t hi s i s no t st e e p enough to
b e regarded a s a r ea ll y s harp en d-po i nt . )
Cd) Ci ) 9 .0 Cmi d - po i nt of pH ran ge)
( ii ) pK " - l og K
a a
K an ti 10 g C- PK 11 . 0 x 10 • mol dm 3 I
a a)

Un1't d e d uce d f rom .. K - [ H' Ca q ) ] [ I n- Ca q ) ]

a - [ HInC a q lj

( e) A col our c ha n g e would j us t begin to be d isc e r n i b l e at 13 . 5 cm' added

ac i d, bu t t he cha n ge f r om blu e to y e l l ow , thro ug h gree n , wo u l d not be
c omp l et e til l 2 2.5 Col " a cid ha d bee n a dded . This i ndi cator i s useless
fo r t his t i t r ati on - th e end-poin t i s no t s~ a rp a nd , in a ny c a s e , doe s
no t co r respo nd with e ithe r o f the eq Ui val en ce poin t s .
 Exerc i s e 46
Exerci s e 4 8
( a) The metho d is t he s ame as i n the Wo rked Exampl e . The pH va l ues , a nd
(a) Ini tial a mou nt of CH,CooH = co ncent ra t ion x vo l ume
inte rmediate answers. a r e s hown below i n t ab ul a r f orm.
= 0 . 10 mol dm- ' x 0 . 0 25 dm' = 2.5 x 10 - ' mol
Vol ume of Amoun t or Amo unt of IExce s s [o H- (aq) ] [W ( a q ) ] Amou nt of CH.COoH at ha lf neu cra l i zaci on point x 10 - ' mo l = 1 . 25
a lka li / em' al Kali /mol acid/mol f mo l / mo l dm- ' / mo l dm- ' pH emo unt
Vol ume of NeOH require d for hal f ne ut r alizat i on = conc ent r a t i on
0 .0 0 .00 250 0 . 00 25 0 - 0 . 100 1. 0 0
5 .0 0 .00 0 50 0 . 002 50 0 .00200 - 0.06 6 7 1. 18 = 1 . 2 5 x 10-' mel = 125 10 - 0 d'
0 . 10 mo l dm-' . x m
10 . 0 0 . 00100 0 .00250 0 .0 01 50 0 .04 29 1 . 37
Total vol ume a t ha l f ne utra l iza ti on poin t
20 .0 0. 0 0 200 0 .00 2 50 0 . 000 50 0 . 01 1 1 1. 9 5
= vo l ume of CH,Coo H s ol ut io n + vo lume of NaOH so lu tio n a dded = 0 . 0 3 75 dm'
24 .0 0 . 00 2 40 0 .00250 0 .00 0 10 - 0 .00204 2 . 69
3
= amo unt = 1 . 7 5 X 10 - 3
25 . 0 0 .00250 0 .00250 1 .00 X 10 - 7 me l = 1 0 . 0 3 3 mo l dm- I
1 . 00 x 10 - 7 7 .0 0 [ CH3 CO • H( a q ) ] vo lu me 0 .0 37 5 dm3
26 . 0 0 . 0026 0 1
0 .00250 0 .00 010 0 . 0019 6 5 . 10 x 10 - ' 11. 3 Since ha lf th e orig i nal acid has bee n ne ut r a l i zed and converted to
1
30 . 0 0 . 0 0 30 0 0 .002 50 0 .000 50 0 .00909 1 . 10 X 10 - • 12 . 0 ethanoa te i ons,
L-
(b) = 10 .033 mo l dm- ' \
14 [bl K = .b.;.:.~~~~~~~...L
a
12 .. = Ka x 1 = 1. 7 x 10 - ' mol dm-'

Ir pH x 10 - ' ) = ~

....... S I I I ! 1 ----4
~+---t-+ - +
o
o
pH
+- Exer ci s e 49
The pH va l ue r ead fr om your c urve sho uld be quite c l os e to 4 . 8 .
6

4
I Exercis e 50
I I I 1P C2 Hs CO. H( aq ) - C. H,CO. - (a q ) + H' ( a q )

K = .J...:..:..~~~~~'i-:-'-=='-'-
0
~ 5 10 15 20 25 30
a
volume of NaO H added /em 3
.. [H'( aq )] =

( c) The most s uitab l e ~ n dicato r would be br omo thymol blu e . = 1 .3 x 10 - ' 1 d -, 0 .1 0 mo 1 dm- ' = 2 6 10 - ' 1 d -.
rna m x 0 .050 mo 1 dm- ' . x mo m
pH = - l og [ W ] = - l og (2 . 6 x 10 - ' ) = - (0 .41 - 5 ) =~
Exercise 4 7 Note t ha t in t his ty pe of calculat i on i t is us ua l t o a ssume tha t t he concen -
trations of f re e a c i d me lecule s a nd an io ns ar e equ al t o t he con ce nt r a t io ns
(a ) pH gr ea t er t ha n 7
ob tai ned fr om t he amo unts us ed to ma Ke the s ol ut ion ; i . e . we assume t hat
CN- ( a q) + HoO (l) p HCN (aq ) + oH- ( a q) a ny te nden c y f or th e disso l ved a c id molec ules t o (ll ';Socia t e i s ba l a nce d by
the tenden c y f or t he dissol ve d anions t o combi ne wi t h hydro gen ions.
( b) pH gr ea t e r tha n 7
CO,O-(a q) + Ho o (l) ~ HCO, - (aq ) + OH - ( e q)
(cl pH greate r t ha n 7
F- ( a q) • HoO( l) ~ HF( aq ) + oH-( aq)
(d ) pH less th a n 7
NH. ' ( e q) + HaOrl ) ~ NH. ( a q ) + H, O'( a q )
 Exercis e 51 Exer c i se 53
(a) + W (aq)
(a ) K
a
K = ~q~~~~,-+,..="'-'-'-
a
_, 2.0 mo l dm-'
[H'(aq) ) = Ka ~~,~z~~'~ ;-~ ;i 1.5 x 10-' mol dm x 0.50 mo l dm-3
[ W (a q JJ = K lo-:2"-;-,l'=:~;'='"i-+ 6 . 0 x 10-' mo l dm-'
a

= 1. 5 x 10-' mol dm-' x : .~ mol dm=: = 1. 5 x 10-' mol dm-' I nit ia l pH = - l og [H'( a q) ) = - (0 .78 - 5) = ~
(b) Amo unt of NaOH add ed = aV = 2.0 mo l dm-' x 0.0 20 dm' = 0.040 mol
pH = -lag [H'(aq)] = - log (1 . 5 x 10- ') = -( 0 .18 - 5 J =@] As suming that all t he added NaOH rea c t s with C, HzCO.H to f o r m
(bJ C,H ,CO. - . the new equ i l ibrium amount s ar e:
[W(aqJ) = 1. 5 x 10- ' mo l dm-' x ~ :~:i ~~=: = 3 .0 x 10- ' roo l dm-'
Amount of C.H zCO. H = (2 . 00 mo l dm-' x 1. 0 dm' ) - 0.040 mo l = 1 .96 mol
pH = -l ag [ H' Leq l ] = - l og (3 .0 x 10- ' ) = - (0 . 48 - 5) =a Amo unt of C.H .CO. - = (0 . 50 mol dm-' x 1.0 dm' ) + 0.040 mo l = 0. 54 mol
(c ) [ H' ( aq J] =
.0 m
1 • 5 x 10-' mo 1 dm-. x 02.50 mol
al dm-'
dm- ' =
60
, x 10-' mo 1 d m-.
[ W (a q )] = K 'r """ Z",u ' ~ l a y } j' = 1.5 x 10-' mo l dm-' x 1.96 mo l/ 1.02 dm'
a C,H . CO. (aq ) 0. 54 mol / 1.0 2 dm'
pH = -lag [ H' ( a q J) = -log (6 .0 x 10-' ) = - (0 .78 - 5J =~ 5 . 4 x 10- ' mo l dm-'
New pH = - To g [H'(aq) ] = - ( 0 .73 - 5) = ~ j-0-.-0-5 - i-nc-r-e-a-s-e'l
( d) [ H' (aq J] = 1. 5 x 10- ' mal dm- ' x 0.
... 50
... roo l dm
. _-'
i 3. 75 x 10- 0 mo l dm-'

pH = -lag [W( a qJ] = - la g (3 . 75 x 10- o J = - (0 .57 - 6) = [:D (c ) Amo unt o f HCl adde d = aV = 0 .50 mo l dm-' x 0 . 100 dm' = 0 . 050 mo l
Assumin g t ha t all the added HCl rea ct s with C. HzCO.- io ns to f or m
C, HzCO . H. t he new eqUili brium amo unt s ar e :
Amount of C. H, CO. H = (2.00 mol dm-' x 1.0 dm') + 0 .0 5 mol = 2 . 05 ma l

K = = .5 0 mo l dm-' Amo unt o f C. H. CO. - ( 0 .50 mo l dm- ' x 1 . 0 dm') - 0 .0 5 mol 0 .4 5 mol
~
1 .7 0 x 10-' mo l dm' x 00 .50 mol dm 3
a
o C. HzCO. H( aq ) • 2 .05 mol /1 .10 dm'
~ 1. 70 x 10-' mol dm- ' [ H''L eq l ] = K 1 .5 x 10- ' mol dm- x 0 .45 mo l / 1 . 10 dm3
a C. H,CO. -( e q l ]
:. init i al pH = - l o g [W( aql) - (0 . 23 - 5) =~ 6.8 x 10- ' mol dm-'
(a) Amount of HC l ad ded = aV 1 .0 ma l dm-' x 0 . 001 0 dm' = 0 . 0010 mal New pH - l og [W( aq ) ] - ( 0 . 83 - 5 ) = ~ 1-0- .-0-5 -d-e-c-r-e-a-s-e'l
As su ming tha t a l l the a dded HCl r eact s wit h CH.CO.- ions t o f orm
CH.CO.H. t he new e qu i l i br i um a mo un t s a r e :
Amoun t of CH, CO. H = (0 .50 ma l dm-' x 0 .10 dm') + 0 .0010 mo l = 0 .051 ma l
.
Amount of CH, CO.- = (0 .50 mal dm-' x 0 .10 dm' J - 0 .00 10 mol = 0. 04 9 mo l

[W ( )J = K [CH. CO. H( aql] = 1 70 10-' 1 d -. 0 .051 mol /0 .1 01 dm'

aq a [ CH.CO. ( aq )] . x mo m x 0 .04 9 mol / 0 .1 01 dm3
1. 77 x 10-' mo l dm- '
-----~
new pH = - l a g [W (aqJ ) = - ( 0 . 25 - 5 J = ~ 1 0 .02 de crea s e I
(b) Amo unt of KOH a dded = aV = 1 .5 mal dm-' x 0 . 0020 dm' = 0 .0030 mol
Assumi ng t ha t a l l th e a dded KOH r eac t s with CH.C O. H to form CH.CO. -
ion s, t he new e qui l i br i um amount s a re :
Amo unt of CH.CO. H = (0 .50 mo l dm-' x 0 . 10 dm' ) - 0 .003 0 mol = 0.04 7 mol
Amo unt of CH.CO.- = [0 . 50 mol dm-' x 0 . 10 dm' J + 0 .0030 mo l = 0 . 053 ma l
[ H'(a )J = K [ C H, co. ~( aq) ) = 1. 70 x 10-' mol dm-' x 0 . 047 mol /0.10 2 dm'3
q a [ CH,CO. ( aq)) 0 . 053 mo l /0. 102 dm
1 .5 1 x 10- ' mo l dm-'
new pH ~ - lo g [ W( a q J] = - ( 0 . 18 - 5 J = ~ 1 0 . 05 in crea s e I
 Exe rcise 54 Exe rc ise 57
( a) Amount of hyd ro gen i o n ~dded ; co n ~ e n t r a l i on x vo lume H K 1 [ ac i d ]
[a)
p , = p a - og [ co nj uga t e ba s e r
• 1 .D mo l dm- ' x D.DD1D dm'
; 1.D X 10 - ' mol [ CH,C0 2H[aqJ] _ _ _
l og [ CH,C0 -(aq)J - pKa - pH - 4 .7 4 - 4 .7 0 - D. 04
2
To te l vo l ume of s o l ut i on after co n t a mi nati on ; 1D1 em' ; D.1D1 dm'
[ CH.C 0 2 H[ aq ) - ' _ ~
H" [ = =
[ CH.C0 [ aq J - an t l l og 0 .0 4 - ~
J] ; amount 1 . D x 1D- ' mol 9 9 10 - ' 1 d -. 2-
[ aq vo l ume 0 . 1D1 dm' • x mo m
i .e : t he s o lu t io ns s ho ul d be mixed in t he rat io 1 . 1 vo lume s o f e t han o i c
pH = - l og[ H' ( a q ) j = - l og ( 9 . 9 x 10 - ' ) = - ( 0 . 996 - 3 J = ~ ac id t o on e vo l ume of s od i um e t ha noa t e .
The pH of the wa t er has decr eased fro m 7 . D to 2 . 0 . i .e . by 5 .D units
[ b) ; pK - pH = 4 .74 - 4 . 40 D.34
(b) Amount of hyd rox id e ion added; conc e nt r a t ion x vo l ume a

• 1 .5 mol dm- ' x 0 .DD20 dm3 •• = a ntil og 0. 34 = ~

= 3.D x 10 - ' mo l
i .e . the s o l ut i o ns s ho ul d be mixe d i n the ra t i o 2 . 2 vo lumes of e than oi c
To t a l volume of so l uti on after co nt a mi na t i o n = 1D2 e m' = D. 1D2 dm3 ac i d to one vol um e of s odi um eth an oa t e .
[OH-( ) ]=~ =3 .0 xlO-·mol ; D02 l d -' Note t hat we a ga in a s sume that , due t o t he pr ese nc e o f etha noate i on.
eq vo 1 ume 0 . 10 2 dm' . 9 mo m t he i o ni za t i on of e t hanoic a c i d is s uppr e ssed . There f o re , t he
K co nc e nt r at i o n of hyd ro g e n ion i s smal l compa r ed to t he co nce nt r a t i on of
w = [ H' [ aq J ] [ DH-[ aq) ] e i t her a c i d o r ba se , so t hat we ca n t a ke i ni t i a l c onc e nt r a t i ons a s
• _ _ Kw _ 1. D X 10- " mo1 2 dm-' _ -1 ' - , being e qua l to e qUi l i br i um con c e nt ra t io ns .
[ H ( aq ) J - [OH-( aq ) J - D. 02 9 mo l dm J - 3 .4 x 10 mol dm
pl-i > - l og [ H '' Leq l ] = - l o g 3 . 4 x 10 - 1 ' = - [D . 53 - 13) = ~
Exe rcise 58
...... The pH of t he wate r has in c r ea se d f r om 7 . D t o 12 .5 , i .e . by 5.5 units
[a ) pK = - l og K x 10- ' ) 3 .8
oI\) a a
pH = pK -l og ~~~~M
Exerci s e 55 a

NH. ' [ a qJ - NH,[ a q) + H'(aq) Si nce pH ; 0

K = rNH,( aq)] [ W ( aq ) ]
a [ NH. -raq ) J mol dm- 3 I
Amou nt of NH.' a dded ; cV = 0 . 20 mo l dm- ' x 0 .75 dm' ; D. 15 mol HC D2 H( a q J ]
(b ) pH = pKa - l og HC0 - (aq ) ]
Amount of NH, ad de d = cV = 0 .10 mo l dm-' x 0 . 75 dm' = 0 . 07 5 mo l 2

I NH. ' ( a q ) ] _ 6 OD 10- 1 0 1 d -, 0 . 15 mol/ 1 . 5 dm' 4 1 = 3 8 -1 HC0 2 H[ a q ) ]

[W ( aq ) J = Ka [ NH, [a qJ ] - . x mo m x 0 .075 mo l / 1 . 5 dmJ . . og HC0 2 -[ a q J]
; 1 . 2 x 10- 9 mo l dm-'
[ HCD 2 H[ aq J )
a n til og [3 . 8 4 . 1) = a ntilo g - D.3 ; ant ilo g [ - 1+ 0 . 7l
pH ; - lo g [W( aq ) ] ; -lo g (1 . 2 x lO- o J ; - [ -9 +0 . 08 ) ; ~ [ HC0 2 - [a q ) ]
= 5 x 10 - 1 or 0 . 5
[HCD 2 - [aqJ] 2[ I-CD 2 H[ e q ) ] 1 1 •0 mol dm- ' I
E xer~i s e 56
K ; [H'[aqJ] [ /q aq J]
HA(a q ) _ H'( aq ) + A-(aq) a r " 1\r l'

[ H" ( aq ) J = K
a

Mu ltipl ying t hrou gh by - 1 : -l o g [W (aq) ] =

si nce -lo g [ H' [a q ) ] = pH a nd -lo g Ka = pKa

 Exercise 59
Firs t. no tice that the exp r e s s i on for pH give n in t he q ues t i o n is in a Exerci s e 60
s lightl y d i f f eren t form fr om t he one we ha ve us ed i n th e Uni t . Howe ve r , th e In eac h cas e . c hoo se a wea k ac i d wi t h a pK va lue c l os e t o t he required pH.
t wo are equivalent becaus e a
(a l Sod ium hydr og en car bo nat e . Na HCo• • an d sodi um carbonat e , Na. Co •.
1 r ba s e - 10 acid
+ og Lac i d g t base ] HCo. - [ aq ) is t he wea k aci d ; pK = 10 . 3
a
[a) The subs ta nce most likel y to change t he pH of t he blood i s ca rbon Co. ' -( a q ) is t he co nj uga t e base
di o xid e o n its way to t he lungs . CO. d i s s olv es i n bloo d to gi ve [b ) Ammonia , NH, ( aq ) , an d ammoni um ch lorid e , NH. C1
ca r bo nic [IV ) ac id, whi ch i s normal l y diss oc ia te d i n s o l ut io n .
NH. '( aq ) i s th e weak a c id ; pK "9 .3
Co.[ g ) + H. o [l ) - H.Co .(aq) NH. [aq) is t he conj uga t e ba se a
H. Co. ( aq ) - HCo. - ( aq ) + H'[ a q J OR
As t he con ce nt r a t i o n of free hydr oge n ions increas e s . t he eq uilibri um Boric ac id , H. Bo. , a nd sodiu m borat e . NaH.BD• .
H. Co .[a q ) - HCo. - [ aq ) + H' [ a q ) H, Bo. [ aq ) is t he weak aci d ; pK = 9 . 2
shi f t s t o th e le ft , r e mo vi ng them from so lut ion a nd pr e ve nt i ng a s ha r p H. BO . - ( a q ) is the conj uga te b as~
dro p in pH. [c) Sodi um hyd r oge ns ulph i te . NaHSo•• a nd s odi um su l phite . Na. So .
( We ha ve a s su med t h r ou ghou t th i s a nswer that t he conce nt r a t io n of HSO,-( a q) i s the weak ac id ; pK = 7 .2
hydr og e n io n pro d uced by t he di ss ociati o n of c a r bon i c( I V) a ci d i s s ma l l a
So. ' - ( aq ) i s t he co nj uga t e ba s e
compare d wit h th e conc e nt r a t i o ns of t he ca r boni c ( IV ) a c i d i t s e l f an d
t he hydr og e nca r bonat e a ni o n . The refo re. we tak e t h e co nce ntra t io ns OR
g i ve n i n t he que s t io n a s eq ui libri um co nce nt r at i ons .) Sodi um di hyd r o ge nphos phat e ( V). NaH. Po . , a nd d i s od i um hydr oge n-
phospha t e [ V) . Na.HPo •.
-.. H.po . - [aq ) is t he wea k a ci d ; pK = 7.2
(b ) [ H' [ a q 1 ] 7.9 X 10- 7 mol dm- ' a
a HPD. ' - ( a q ) i s th e co nj uga t e bas e
co pH -l og [ H' ( a q J] = - l og [ 7 .9 x 10- 7 ) - (0 . 90 - 7J 6 .10 ( d) Et ha noi c a ci d . CH,CD.H . a nd s odi um e t ha noa t e . CH .C D. Na .
ba se CH.C D. H[ aq ) i s t he weak ac i d ; pK = 4 .8
pH = - l og Ka + l og t a c i d] a
CH.C D. -( aq) i s t he c on j ugat e bas e
6 . 10 = - lo g Ka + ° [s i nc e [ ba s e ] = [a c id])
l og Ka =~
( c) ~ base ]
pH = - l o g Ka + lo g aci d ]

7 .4 = - ( -6 . 10 ) + l og Ld
aCl
ffilli
10 g t abac si de J] -- 7 . 4 - 6 . 10 1. 3

~J
.[aCidJ = a ntil og 1. 3
~
[d ) Sinc e th e r a t i o of conce nt r a t i o ns of base to a c i d i s 20 : 1,

[ ba s e ] ;~ x 2 . 52 X 10-' mol d m-' 12. 4 x 10-' mol dm- ' !

[a cid ] ; 1 x 2 . 52 x 10-' mo l dm-· 11 . 2 X 10-' ~~~

 Ex pe r i me nt 7 Spec ime n r e sult s a nd answe rs t o ques ti o ns
Exerci se 61
1. Fr om t he su bst ance s av a il a bl e, t he a cid with a pKa val ue neare s t to the
(a ) ( il B
req uired pH of 5 .2 is ethano i c aci d, pKa = 4 .8.
( ii ) The o H-(aq) i on s r e ac t ed wi t h e t ha noi c a c i d mo l ec ule s to f o r m
pH = pKa - log ethanoa te ions and wa t e r :
OH-(aq) + CH.Co .H [aq) ~ CH,CO . - [aq ) + H.O [ l )
ant il og ( pK - pH) = antilog ( 4 . 8 - 5 .2)
a Thi s remo ved most of the adde d hyd rOXide i o ns f r om solution and
an tilog [ - 0 . 4 ) = 0.40 prevented a l a r ge change i n pH.
If X cm" of 1 . 0 M CH.CO .H is used to make 100 cm' of bu f f er , I I [ b ) Et hanoat e i o ns i n s o l ut i o n tend t o accept proto ns to form t he wea k acid
(1 00 - x )cm' of 1 . 0 MCH,Co. Na is required. e t ha noic acid :
x
100 _ x = 0 .4 or x = 40 - 0 .4 x CH.CO . - (aq ) + H' ( a q ) ~ CH.CO. H(aq)

40 Thi s r emova l of pr otons reduces t he ir co ncentrat i o n be l ow

x = 1":4 29 1.0 x 10- 7 mo l dm- · [ a nd correspondi ngl y increas es the co nce nt r a t i on
of hydr ox i de i ons ) wi t h t he resu lt t hat the p H rises abo ve 7 .
:.:1 us e 29 cm' o f 1 .0 M CH. Co. H and 71 cm' of 1 . 0 M CH . CO.Na
(c ) The pH of B woul d ha ve bee n ve ry l i t t l e alt e red i f i t ha d be e n diluted
2. From th e substances availab le , th e a ci d wi th a pKa va l ue neares t to t he
wi t h wa t er . It wo ul d hav e stayed very c l o s e t o 4 . 8.
r equir ed pH of 8. 8 is t he ammoni um i o n , pK = 9 . 3 .
a [d) (i ) Fro m t he t a bl e , t he pH of 0 . 01 M ethanoi c acid i s 3 . 4 , i . e .
[ NH. ' [ aq ) )
f . " . •• \ = antilog ( pKa - pH) = antilog ( 9 . 3 - 8 .8 ) -lo g [W [ a q) J = 3 .4
antilog ( 0 . 5 ) = 3.2 [W[ a q ) ) = a ntilog [ -3 . 4 ) = an til og ( -4 +0 . 6)
If x cm' of 1.0 M NH.Cl i s use d to ma ke 100 cm" of buffe r, [ 100 - x) cm'
14 .0 x 10-' mo l dm-' I
of 1 .0 M NH, i s req uired .
x ( ii ) Vi r t ua lly a ll th e hydrog e n i o ns i n s o l ut i on come f rom the
3.2 or x = 320 - 3 . 2 x
--.I.
100 - x ion i zat io n of et ha noi c a cid ,
a x 76
CH. Co.H ( a q ) ~ CH. Co.-[aq) + H' ( aq)
~ = -4320
.2-
[ CH. Co . -[ a q ) ) = [ W ( aq ) ) 14 .0 x 10 - ' mo l dm-' !
:. ~7 6 cm' of 1. 0 M NH.CI a nd 24 cm· of 1 . 0 M NH• .
K = [C H. C02 - (a q ) J [ H' (a ql) (4 .0 x 10-' mo l dm- ' )'
3. Meas ured va l ues shou ld be wi t hi n 0 . 2 un i t s of the r e qUi r ed va l ue s . ( ii i)
a [ CH.C0 2 H[ a q ) J 0 .0 10 mo l dm 3
Di ffe renc es ma y be due to i na cc ur a t e pH mete r s but, in an y ca s e , t he
soluti on s us e d are t oo co nce nt r a ted fo r th e e qu i l ibr i um law to be ap pl i ed = 11.6 x 10-' mo l dm- ' I
preci sel y us in g conc ent ration s . pH met ers a ctuall y measure - lo g [ a c tivit y
of hydrogen io ns), where ' a ct i vi t y' is th e techni ca l term for ' e f f e c t i ve (e ) Any weak a ci d wi t h a pKa valu e c l os e t o 10 , to ge t her wi t h its
concen t r at io n ' . At hi gh c onc ent r a t i ons , i ons i nte r a c t wi t h each other so co nj uga te bas e , wou l d be suitab l e; e .g . ammon ium c hl o r i de ( co ntai ni ng
th a t t he ir e f fec t i ve co nce nt ratio n i s r ed uc ed - as a re su l t , pH met ers NH. ' ; pK = 9 .25 ) an d ammonia s ol ut io n ,
a
t e nd t o r ecor d hi ghe r va l ues than yo u mi ght ex pec t fo r concen t ra ted
so l ution s .
4. The equat i o n use d i n th e ca lcu la t io n s ugges ts th at t he pH de pe nds o nl y
o n t he r a t i o of c o nce ntra t io ns of a cid a nd conj ugat e ba se. so tha t
d i l ut ion-shOul d hav e no e f fec t . I n pra c ti c e , t he pH of t he s e buff ers
f a l ls a l i t t le with di lutio n - be twee n 0 . 1 a nd 0 .2 unit s f o r a 10:1
dilu tion. Aga i n , t hi s i s du e t o the fa c t t ha t meas ur ed pH de pen ds on
a c tivit y, whi c h c ha nges wit h co nce nt r a t io n , a nd a lso to the brea kdown of
t he as s umpt ion s made i n th e ca l cu lation . e .g .
[ CH,CDoH[ aq) J ~ mo l ari t y in dil ut e so luti ons .
5. The ca pa c i ty of the buf f e r s fa ll s dra mat i ca l ly with dilution . The
concentrated buffers will a bsorb 10 em" of 0. 2 M HCI or 0 . 2 M NaoH with
a pH c ha nge o f on l y 0. 1 o r 0. 2 units . A s imilar c hange f or buf f er s
di luted by 10 : 1 i s bro ught ab ou t by o nly 1 cm" of a cid or a lkali ; whi l e
f or buf f er s dilut e d by 100 : 1 a s ing l e drop o f a c id or alkali i s enough .
6. Ammoni a i s so vo l a t i le t ha t t he compos it io n of t he buff er wi l l not
r emain co nst a nt .
 Exper i me nt 8 Spec imen r e s ul t s a nd ca l cula tio ns Exer ci s e 67
4 pH = - l og [H "( a qJ ]
Me thod 1 Bes t colo ur ma tc h wi t h tub es c or re spo nding t o =6
l og [ W( aqJ ] = -p H = -1. 11
.. pH = pKI n = 4 . 0 - l og 6"4 = 4 .2
[ W (a qJ] = a nt ilo g ( - 2 +0 .8 9 ) = 17 . 76 x 10- 2 mo l dm- ' !

pH = pK -log ~..,..,..""'""~;.=~
a
Exerci s e 68
4 .2 = pKa - 0
pH = -l og [ H'( a qJ]
• . pKa = 4 .2 a nd Ka = dm- ' 1 l og [ Ht Ceq l ] = -p H = -5 . 64
2 .0 cm
Me thod 2 Bes t colou r mat c h whe n cor respo nds t o 3 .0 c m [ W (a qJ j = a ntil og ( - 6 +0 . 36 J = [ 2. 29 x 10- ' mol dm- 'I

.. pH = pK = 4 .0 4 .2
In
Exerc is e 69
pH = pKa - l og ~"""'SL.::';'='"i-+ pH = -log [ H" (aq ) ]

4 .2 = pK - 0 = [ C.H.CO. -[aq )]) log [H' (aqJ J = - pH = - 7. 71

a
[H'(aq ) ] = ant il og (-8 +0. 29 ) = 11.95 x 10- 8 mol dm- 3 !
.. pK = 4 .2 a nd K = a nt i l og (-4 .2 ) = 16.3 x 10- ' mo l dm-' I
a a
Exer c is e 70
....L
pH = -log [ W (a qJ]
Exerc i se 62
~ lo g [ H" [ aq ) ] = -p H = -3 . 40
pH = -log [ W( a qJ] = - lo g ( 8 . 34 x 10- ' ) = - ( - 3 +0 .921 ) = ~
[H"( aq) ] = ant ilog ( - 4 +0.60 ) = 3.9 8 x 10- ' mo l dm-'

= [CH. C02 - (a qJ ] [ H' [aq J) = ( 3 .98 x 10- ' mol dm-3 ) .

Exe r c ise 63 K ( 0 .010 - 3 .9 8 x 10-' mol dm 3
a [ CH"CO. H(a q J]
pH = - l og [ W (a q ) ] = - log (2 .6 2 x 10- 8 ) = - ( -8 +0. 418 ) = ~ 1 .5 8 X 10- 7 mol · dm- ·
= =11 . 6 5 x 10- ' mol dm- ' I
0 . 00 96 mo l dm 3
Exe rcise 64
Si nce ni tric aci d, HN 0 3 , i s a strong a ci d we can a ssume i t is f ul l y Exe r c i s e 71
di s soc ia t ed, and [ H' ( aq ) ] = 0 . 54 mol dm- 3 •
pH = -l og [H"(aq J]
pH = - l og [ H' (a q)j = - l og 5 . 4 x 10- >' = - (-1 +0 .7 32J = ~
log [ W( aqJ ] = -pH = - 2 .40
[H'( a q ) ] = a nt il og ( -3 +0 . 60 ) = 3 .98 x 10- '
Exerci se 65 ( 3 . 98 x 10- ' mo l dm- · )·
K
= [ HCO.- ( aqJl [ H' ( aqJl =
pH = -log [H"( a qJ] = - l og [ 2 . 23 x 10- 3 ) = - ( -3 +0. 348 ) = ~ a [ HCO. H( aqJ ] (0 . 10 - 3 . 98 x 10- 3 ) mol dm 3
2
1 . 58 x 10- ' mo 1 dm- ·
= = 11. 65 x 10- ' mo l dm- 3 1
0 .096 mo l dm- '
Exerc ise 66
pH = - log [ H"( a q J]
l og [W ( a q J] = - pH = - 11. 11
[W [ aq ) ] = a ntil og ( - 12 +0 . 89) = 17 . 76 x 10- 1 2 mol dm- 'I
 Exerc ise 72 Exe r c i s e 76
pH = - l og [ H' (aq) ] K = .L.:.~~H-,;"=':+<~~ •• [H '( aq)) = K
a a
l og [H ' Teq l ] = - pH = -4 .0 3
Making the usua l assumpt ion tha t in a buf f er so l ut io n. t he equ il i br ium
[ H'( a q ) ] = a nt i l o g (- 5 +0. 9 7 ) = 9 .33 x 10-' mol dm- ' c oncentrat ions a re equal to th e concentrations on mixing:
_ [H '(aq)] [ HS- (aq)] (9 .33 x 10 - ' mol dm- ') 2
K = (a)
a - [ H2 S( a q )] (0 . 10 - 9 .33 x 10- !) mo l dm- ' [ W (aq) ] = 1 .6 x 10 -· mol drn- ' x °1.~0 m":ll d~m_~' = 1 .6 x 10 - ' rrol dm- '
0 2
~ 8 .70 x 10 - mol dm- · = 18 7 10- 8 1 d -. I pH = - log [W(aq)] = - log (1.6 x 10-' ) = - ( -5 +0. 20 ) = ~
0 .10 mol dm- ' . x mo m
[ b) [H ' ( a q ) ] = 1 . 6 x 10-· mo1 d m-. x 02.0
.20 mo
mol 1 dm-
dm-3
' = 1 . 6 x 10 -' mo 1 d m-.

Exe rcise 73 pH = -Lcg [W(aq ) J = - l og ( 1 .6 x 10 - ' ) = - ( - 3 +0 . 20) = ~

= [ W (aq l1 f ClO - ( a q )]
K (c ) [ H' ( )] 1 6 10-· 1 d -. 0 .5 0 mol dm- ' 3 2 10 - ' 1 d -.
a l HCl O( a q ) J aq = • x mo m x 2 .5 mo1 dm- ' = • x mo m
3 7 10- 8 1 -. _ ( x mol dm- ·) · _ ( x mol dm- ') 2 pH = - l o g [ W(aql] = -l og (3 .2 x 10 - ') = - ( -5 +0 .51 ) = ~
• X mo dm - ( 0 . 0 10 _ x) mol dm- ' - 0 .010 mol dm- '
8 10
:. x 2 = 3.7 X 10- x 0 .0 10 = 3 .7 X 10- and x = 1 .92 x 10- '
pH = - Tog [ W ( aq ) ] = -l o g (1 .92 x 10 - ') = - ( -5 +0 .28) = ~ Exercise 77
K = [NH.( a q ) ] [ H'( a q ) J .. [ H'' Leq l ] = K ...,:..;.:-,"-.,,:..::.::;..:,.<.
a [ NH. '(aq) J a
Exercise 74
Amoun t of NH. Cl = 1.5 mo l dm- ' x 0.1 00 d m' =
_ [ W ( a q ) ] [ H2 BO . -( aq l)
...... K Amo un t of NH. = 0 .6 0 mol dm- ' x 0 .100 dm' = 0. 060 mol
a - [ H. 00. ( a q ) ]
o Onc e aga i n , we assume t ha t the equil ibr ium amounts i n a bu ffer s ol ution a re
0'> 5 8 10- 1 0 1 d -. = ( x mol dm-' )2 ~
( x mol dm- ') 2
· x mo m ( 0 .0 10 xlmo l dm • 0 . 0 10 mol dm- ' equa l t o the added a mo unt s .
: . x 2 = 5 . 8 X 10- 1 0 x 0 . 010 = 5. 8 x 10 - 12 a nd x = 2. 41 X 10 - 6 1 0 0. 15
.. [ H' ( aq I] -- 5 . 6 x 10- mo1 d m-. x 0.0 60 mol/0
mol/0 .200 dm3 -
. 200 dm' - 1 • 4 x 10-' mo 1 d m•
pH = -l og [W[aq)] = - l og ( 2.41 x 10- 6 J = - ( - 6 +0 .38 ) = ~
pH = -log [W( aq) ] = -log ( 1.4 x 10 - ' ) = - ( -9 +0. 14 6 ) = ~

Exercise 75
_ [H'(aql ] [ F-(aq)]
K [ HF(a q J]
a -
r :1 ,
.. [ H'( a q ) ] -- Ka x [H.PO. I ,.-.,-,
Ka -- -(a q)~ ],
5 6 10- . 1 d -. = (x mol dm-')2
• X mo m ( 0 . 0 10 x)mol dm- ' Amount of NaH2 PO. = 2 .0 mol dm-' x 0 . 500 dm' = 1 .0 mol
Amo unt of Na2HPO. = 0 .50 mol dm- ' x 1 .00 dm' = 0 .50 mol
Co = 0 . 010 _4 = 18 < 1000
5. 6 x 10 :. a quadra tic e quati on must be s o lve d
Ka Again, we ass ume that t he equilibrium amounts in a bu ffer solution are e qual
t o t he added amo unt s.
x 2 = 5 .6 x 10-· x (0 . 010 - x)
' ( )J=62 10- 8 ld - ' 1 .0mo l/1 .5dm' = 1 2 1 0 - 1 mol dm- '
x 2 + (5 .6 x 10 - ·)x - ( 5 .6 x 10- 6 ) = 0 .. [H aq . x mo m x 0 .50 mol/1.5 dm' . x
1
pH = - log [ W ( a q )J = -log (1 .2 x 10 - ) = - (-7 +0.08) = ~
x = - 5. 6 x 10 - · ± ~ ; 10- 1 + (2 .24 x 10 - ' ) = 2 .1 X 10- '
or
- 2 • 7 x 10 - ' [abs urd r oo t ! )
pH = -Tog [W (aq)] = -log (2 .1 x 10 - ') = - (-3 +0. 32 ) = ~
( The a ppr o xi ma t e method gives pH = 2. 63 .)
 Exer c i s e 81
K = '>"--=-,..~~~f--'o.-;-r :. [W (aql ) = K x "",,",..,.=-,~-::+'=i-+ K = [ C. H. COa -(aqJ) [H' ( aq) ] . [W( J] = K ~Ca H.Co a H (aq)l
a a a [C.H .CO. Hfa ol l .. aq a x - " -- • ,
Initia ll y, [W ( aq )] = 1 . 7 x
(a ) [ b T eq l ] = 1 . 3 x 10- ' mol dm-' x ~ :;~ :i ~~=: = 3 .25 x 10- ' mo l dm- '
= 3.4 x 10- ' mo l dm- '
pH = - log [H' (aql ] = -l og ( 3 , 25 x 10- ') = - ( - 5 +0 .51) = ~
pH = - l og [H ' ( aq ) ) • -log (3 .4 x 10- ' ) - (- 5 +0 . 53) = ~
( b) Amount of HCl adde d = 0. 10 mol dm- ' x 0 . 0050 dm' = 0 , 000 50 mol
( a lt e r nati vely , pH = pK -log = 4 .8 -log 2 4 .5 ) Ass um i ng t ha t v i rtually a l l th e add ed HCl r eaet s wit h CaH.COa - ion s
a
to form CaH. COaH ,
The amount of ad ded HCl = 1 .0 mol dm' x 0 .010 dm' 0 .0 10 mol
amount of C.H.CO. - = i nitial amount - amo unt r ea c t ed
Assumi ng tha t v i r t ua ll y a ll the a dded HCl rea e ts wi t h CH.C Oa - i ons to form
CH. COa H, ( O. 5U mol dm- ' x 0 , 0 10 dm') - 0 .00050 mol

a mo unt of CH,Co . - in it ia l amount - amo unt a dded 0 , 0045 mol

200 e m' amo unt of C. H5C o. H = (1 .25 mol dm- ' x 0 . 01 0 dm' ) + 0.0 005 0 mol
( 0 .5 0 mo l x 2000 em') - 0 .01 0 mol = 0 .040 mol
0 .0130 mol
200 em' .01 30 mo l / 0 . 0 15 dm'
amount of CH ,CO.H = (1 .0 ITo l x ~~~~ _ 3 ) + 0 .0 10 mo l = 0 , 11 mo l [ H' ( eq l ] 1 . 3 x 10 - ' mo 1 d m- , x 00 .0045 mol /0 . 015 dm3
• 0 . 11 mo1 10 . 20 dm' 4 .7 x 10-' mol dm- ' 3 .7 6 x 10-' mol dm- '
[H '(aq)] = 1. 7 x 10- ' mo l dm- x 0 .040 mo l /0 .2o dm 3
pH = - l og [ H' ( a q) ] = - l og ( 3 . 76 x 10- ' ) = - (- 5 +0 .58) = ~
pH = - l og [ W[ aq )) = -l og (4 .7 x 10-' J = - ( -5 +0 .6 7) = B (e ) Amo unt of NaOH add ed = 1 . 0 mol dm- ' x 0 . 0010 dm' = 0 . 0010 mo l
Thus , t he pH i s lr edu e ed by 0 . 2 units . I Assuming t ha t Virt ua l l y a ll the ad ded NaOH re a c t s wi t h C.H 5C O.H to
-' fo r m Ca H. CO a -,
o-....j amount o f CaH. CO. H = in itial a mo unt - amo unt r eac t ed
Exe rc ise 80 (1 .25 mol dm- ' x 0 ,0 10 dm') - 0 . 00 10 mo l
Ka 0 . 01 15 mol
amo unt of CaH.Co a - (0 . 50 mol dm- ' x 0 .010 dm') + 0.00 10 mol
Ini ti a l amo unt of CH,CO.H 1.5 mo l dm-' x 0 . 50 dm' = 0 . 75 mol
= 0 ,0 060 mol
I ni t i a l amount of CH . CO. - = 0 . 50 mol dm- ' x 1 , 0 dm' 0 . 50 mol
[H ' ( aq )] = 1 , 3 x 10- ' mo 1 dm-, x 00 .011 5 mol/0.0 11 dm' = 2 49 10- '
[H ' ( aq)j = 1 .7 x 10-' mo l dm- ' x ~ .:~ mo: ~~ . ~ ~m: 2 .55 x 10- ' mo l dm- ' .006 0 mo l/0 . 011 dm 3 . x
pH = -log [ H' ( a q ) ] = - l og ( 2 . 49 x 10- ') = - ( - 5 +0 , 40) = ~
pH = - l og [H'(a q) ] = - l og (2 . 55 x 10- 5 )
= - ( - 5 +0 .41) = ~
The a mount of ad ded NaO H = 0 . 10 mol dm-' x 0 . 050 dm' = 0 . 0050 mol
Ass uming t hat v i rt ual ly al l th e a dded NaOH r ea ct s wi t h CH,C O. H to fo rm Exercise 82
CH,CO. - i on s ,
pH = pK - l o g
a
amo unt of CH.C O.H = i niti a l a mount - amount react ed
~~~~~~ = pKa - pH = 4 . 9 - 4 .0 0.9
150 em:
( 0 .7 5 mol x '"__ , ) _ 0 . 005 0 mol 0 ,0 70 mo l

_ 150 e m' an til og 0 .9 = 7 .9

amount of CH.CO. = ( 0 . 50 mo l ' x 1500 em' ) + 0 , 0050 mo l = 0 . 055 mo l
Assum ing that , in a buffer so lution , the e qui l ibrium amount s ar e equal to
[ H' ( a q ) ] -- 1 . 7 x 10-' mo 1 dm -, x 00 .07 0 mo l/0 .20 dm' _ -. -, t he amo unt s dissol ved, t he s olution s ho ul d be mixed i n the ra tio 7 .9 pa rts
. 055 mo 110 . 20 dm3 - 2 . 16 x 10 mo1 dm of pro pa noi c a c id t o 1 part of sodi um pr o pano at e .
pH = - l og [ W( aq)] = - l og ( 2 .1 6 x 10- ' ) = - ( -5 +0 . 33 ) = B Volume of 1 .0 M CaH.Co a H = 100 em' x ~ :~ = 1 69 e m' l
Thus. t he pH is linereas ed by 0 . 1 un it s. 1
Volume of 1 ,0 M Ca H. COaNa = 100 em' x ~ :~ = ~
 Exercise 83 Exerc ise 86
K
w
_ [ HA (a ql] (a ) K K ( HCN ) = 4.9 x 10- l 0 mol dm- '
pH - pKa - log [ A- (a q J) h Ka a

. [ Hpo. '- (aq) ] _ _ 1 . 0 X 10- l • mol' dm- 6

.. log [ po. 3- ( aq )] - pKa - pH - 12 .4 - 11 . 8 = 0. 6 Kh = 4 . 9 x 10- 1 0 mol dm- ' 2.0 x 10- ' mol dm-'

. [HPO. ' - ( a q)] _ 'I 0 - '0 I nit i a l

. . [ PD. ' ( a q l ] - e nt ; og .6 - 4. 0 .0 10 0 0
co ncn/mol drn"?
CN- ( a q 1 + H. 0 (l 1 ~ HCN( a ql + oH- (aq)
Ass uming t ha t , i n a buf fe r so lution , th e equi li bri um amounts a re e qual t o
Equ ili br i um
the amount s dis so l ved , the solut i on s ho uld be mi xed i n t he ratio 4 par t s of 0 .01 o -x x a:
c on c n/mol dm- '
Na 2HPO . t o.1 pa r t o f Na. PO• .
K = [ HCN[a q ) ) [ OH- ( a g ) ]
Vol ume of 0.50 M Na2HPo . = 200 em' x ~ = 1160 cm' I h [ CN-(aq J]
2.0 x 10- ' mol dm- ' = (x mo l dm-') [x mol dm-')
Vol ume of 0. 50 M Na 3Po . = 200 cm' x ~ = 140 c m3 I (0 . 010 -x l mol dm •
Assu me ( 0 .01 0 - x) ~ 0. 010
,
Exerci s e 84 2 . 0 x 10- ' = 0~01 0

H = K - 10 [ aci d~ x' = 0.0 10 x 2 .0 x 10- ' = 2 .0 X 10- 7

p p a g [co nju ga te bdseJ
x = 1 2 .0 X 10- 7 = 4 .5 x 10- '
· [ NH. ' ( aq )) _ _ _ _ _ _
.. log[N H q)) -pK a pH- 9 . 3 9 .5 - 0.2
3(a : . [OH-( a q) ) = 4. 5 x 10- ' mo l dm-'
K l 2
-' ..· [[NH,(aq
NH. ' (aqJJ )) -- a nt t' I og ( - 0 . 2 ) -- a nt I' I og ( - 1 +0 . 8) -- 0 . 63 1 . 0 X 10- • mo 1 dm- · = 2 .2 x 10- l l mol dm-'
o [ W(a q )] = [O H Zaq l] 4 .5 x 10- ' mol dm 3
CO [ NH.'( a q J] = 0 . 63 x [ NH,[ a qJ ] = 0. 63 x 0 .40 mo l dm-' I
= ~5 mol dm-3 pH = -l og [ W ( aq)] = - log ( 2 . 2 x 10- ") = ~
K
fb) K = -Y:!- Kb (NH . ) = 1 .8 x 10-' mol dm-3
h K
Exercise 85 b
l 6
_ _ [ HA(aqJ) 1 .0 X 1o- • mol ' dm- = 5 . 6 x 1o- l 0 mol dm -3
pH - pKa lo g [ A ( aq)) Kh = 1 .8 x 10-' mo l dm- 3

· 1 [ HC0 2H( aq) ) Initial

~ 1 .0 0 0
pKa - pH = 3. 8 - 4. 4 = -0 .6 co ncn/mol dm- 3
.. og [HCO. - ( aqJ]
NH. " ( e q ) ~ NH. (aq) + W(a q l
:. = a ntilog ( - 0 .6 ) = a ntilog ( - 1 +0. 4) 0 .2 5 Equ il ib rium
t~~~:Hi : ~ n ~ 1 . o -x x x
co nc n/mo l dm- '
[ HCo - ( )) = [ HC 02H(aq ) ) = 0 .8 0 mo l dm-' = 1 3 . 2 mo l dm-' I K = [NH3(a q)) W ( a q) ]
a aq 0.25 0. 25 h NH. '( a q)J
5 . 6 x 10 - l 0 mol dm-' = (x mol dm- ') (x mo l dm-' )
(1 .0 - x) mol dm •
As s ume ( 1 .O- x ) ~ 1.0

. • 5 .6 X lO - l o _ x'
- 1:0 "
x = I 5 . 6 x 1o - l 0 2 . 4 x 10- '
[W(aq )] = 2 .4 x 10- 5 mo l dm-'
pH = - l og [H' ( a q ) ] = -l og (2 .4 x 10- 5 )
~
 Kw
(e ) K K (c f) = 5. 6 x 10- 0 mo l dm-'
h Ka a
10
1 .0 X 10- mol ' dm- · • 1.8 x 10 - 1 1 mo l dm- '
Kh = 5.6 x 10 - 4 mol dm- 3
I nitia l
eo ne n/mol dm- ' 0.020 0 0
F-( a q) + H, OD J + HF( aq) + OH- ( a q )
Equil i brium
eonen/mo l dm- ' 0 . 020-x x x

11 ( x mo l dm- ' )
1.8 X 10- mo l dm- '
( 0 .020 -x ) mol dm- :O
(0 .020-x) ~ 0 .020
11 x'
. , 1.8 X 10- = 0 .020

x = 1 3 . 6 x 10 - " = 6 .0 X 10 - 7

:. [ OH- ( a q l ] = 6 .0 X 10- 7 ma I dm- J

K 1. 0 X 10- 1 0 mol 2 dm- ·
1.7 X 10- 8 mo l dm-'
-a. [W ( a q ) ) = [ OH ~aq) ] v • v
" n~ ~ 10- 7 mo l dm- '
o
<0 pH = -log [ H' ( aq ) J = - l og ( 1 .7 X 10- 8 ) = ~
 14 ,
·..... ,I,..

13I 0.10 M NaOH

· .,

I i :~_. i _·:· - ~ ···- t··

' , , I
12
1. ,
· ,
"'.-•... ~

;
'
· ._.. .. i:.jl:~ .., ..; ..
11, .•... i· ,··!··;···,· .~
., .
. ; . i;~;
10) :
....... . :. :. ! r., ;.:.' . . .' .. •... ; • .. :.L.:.. L
~ " l
0.10 M NH 3
,,. pH changes during titration of
; .... . ~~:L r r: , .. ~ . ' 1' .-~ ..
99 ·:"-'-"-'T.' 25 cm 3 0.10 M HCI or 0.10 M CH 3C0 2H
, . .., ... with 0,10 M NaOH orO.10 M NH 3
" ..."' ,..... •.. >. , ; I','
,~" --. , , . .... ; ~ :; .
8I ,., :; ., ... ;; , :... :: .:..
H
· , LI i
... ; ; ;; .. .

......
· . :: :"', r .....I: : , L
...... pH 77 , , H : , ' ; ,.
o ... : '. ,: " .
+
·, it .;..
· '.' .: :: I·:, ;i' 'f"
6i '1 .,. i
, , , ". "J i' "
I : : : : :i L L
; .i.
5il .. ..:.,:::.... 0.10MCH 3C0 2 H L
.; + j
;
. , .. ~
· .
,., ·f /U8' 1 ,. ; , . ' ;
4~
..... .,
, ! ,.;;' , : .:
. .'. ;., ; ,. .; ,.... . I,. ,
/ 7"r:;;... .. " i'"
3I ..
. , . . " , '" .I; +1' ft .' ·i···
.: ... ,
: ' 1 .. 'f,'
' t. ;.;., I'
.
•. 1
21 · ,... I .;... ~L'
;" i T :
, :. ' 0.10 ~ HC' ,.IT:,L '-'-
,,'i" .... , '
, T
., ,: ' .; ; , : .r.. ' ..'.. ,..
;. .;.
'" , .;·,:i;, ,t , I Ll -T I'" ~
,-

o 5 10 15 20 25 30 35 40 45 50
volume of alkali added/emf
CONTRIBUTORS
Project Director
Colin Robertson , Inspector for Science , ILEA

Writing team
The materials were written and revised by practising teachers seconded to the
Project for limited periods :
Lambros Atteshlis Frank McManus
Lesley Bulman Leona rd Roselaar
Mike Foley Fran Rowe
Ann Friend Alec Thompson
Lawrence Halstead Steve Wa xman
Terence Kelly

Production Team
Tony Langham i/c production and cover design
Vanda Chan Graphics
John Sangwin AVA Technician
Peter Faldon AVA Technician
Dawn Devereux Office and typing
Constance Godfrey : Typing
Stella Jefferies Typing and layout
Videotapes
Brian Babb, Producer, Educational Television Centre , ILEA

Reader
John Stephens , Department of Natural Sciences, South London College

Evaluator
John Gilbert , Institute for Educational Technology , University of Surrey

ILPAC trial schools

The following schools and colleges took part in the trials of the Independent
Learning Project for Advanced Chemistry . The Inner London Education Authority
wishes to thank the teachers in these schools and their students for their help .

Abbey Wood School John Roan School

Acland Burghley School Ladbroke School
Bacon's C.E . School London Nautical School
Brooke House School Morpeth School
Dunraven School North Westminster Community School
Elliott School Quintin Kynaston School
Eltham Hill School St . Mark's C.E . School
Ensham School Sydenham School
Forest Hill School Thomas Calton School
Highbury Grove School Walsingham School
Hull College of Further Education Woodberry Down School
Hydeburn School. Woolverstone Hall