r r

r


r r

r






r



r

r r r r

r r
r r


s

r

P
r



P
t

t P

q r tt s

q
t

t t

P P t t

P P t t
 viii

s


s



11













P





P

P
-




P






P
t



P
P
q
r s q
q
PP














P P




P


r rr


q s
q t
P
P s,p,d,f
q
r
q P q
q
q
P
q

 xii

U H

r
H

P P

P P

P K, Q G

I-IV

P
SOME BASIC CONCEPTS OF CHEMISTRY

q rs

t r






SI

t
















2

P















(AZT)




qrst r t s rrs rr




(stratosphere)
(Ozone depletion)
(CFC)

(i)

(ii)

(iii)





 3

s
t





s

t
s

s

s

t
P


r






q q


r

s
t P

s

t s
t

4

P 6 m

m P P
(H 2O) (CO 2 ) P

t
(the English System)
(the Metric System)

P P
P P

P P

P
(SI)

P P Le System In-
ternational d'Units), S.I. P

(pop)
P (conference Generale des Poios et
Measures, CGPM) CGPM





P

SI


qrs
P P
P SI
P
P P SI P
P P


P
P

P
P P P

P P
 5

r r

SI SI
l m
m kg
t s
P I A
T K

n mol
Iv cd

r SI

qs qt


q qs q

q qs 133 P


qs P
P
2 107

q q qs P


t qs qs q
(elementary entities) kg
P
(mol)

(specify) P P

tt qs
540 1012



6

t t

t




P NMI t
t
t
NPL

t
t


t
r SI r r qs

SI
1024 y
1021 t z 1 = 1000
10 18
a
10 15
f
1012 p

109 n
106 SI
103 m m3
102 c
10 1
d cm3 dm3
10 da
102 h (L)
10 3
k SI
10 6
M 1L = 1000 mL 1000 cm3 = l dm3
10 9
G
1012 T
10 15
P
10 18
E
10 21
t Z
1024 Y

 7

SI

SI =

kg m3


g cm3 (g)
cm3

C
F K
K SI

0 100

P 32F 212






qst
0C

qrs
t t t
t
t 2g



t

g
t t
t t
t t
(Pt-Ir) t t
t t
t
Pt-Ir t t
t t
t
t

t t

N 10n

n t

t N t
N
t
232.508 2.32508
10
2

Pt - Ir P t t
t
P t 1.6 104 t
t t
0C (273.15 K) Pt-Ir t t (4)
t
t

t t
(Laser)
1.65076373106

t
CGPM







 9

/g
1 2 r (g)

1.95 1.93 1.940
r
1.94 2.05 1.995

2.01 1.99 2.000

r rr
r tr q
P
r t r r q rr
r r tr
r r q s rr r tr
t t r q r 11.2 mL
r 6.65 104 8.95 103 r r 11 r 2 r
r r r 1 rr q
tr sr r r 1
rr r tr q
6.65 104 + 0.895 104
r q t
s t t r
t
(6.65 + 0.895) 104 = 7.545 104 (1) r q
t r 285 cm r 0.25 mL
2.5 102 4.8 103 q
= (2.5 102) (0.48 102)
(2)
= (2.5 0.48) 10-2 = 2.02 102
rq r
srr q r

q
rr
(3) r r q
r r r q
q ts sr r rs r
(4) r
tr q
r r r

r q
r r q r r r
r rq
r r q q
2.00 g r r r
1.95 g 1.93 g r r q q r r
sr r r r q
q 2
1 10 , 1.0 10
2

1.94 g 2.05 g r r q 2
r 1.00 10 r q
r q r (5) r r
2.01 g 1.99 g r r
r q q r
1.4 t r q s r r t r
10

t
2 = 2.000000 20 = 20.000000 qsq


4.01 102 8.256 103


(factor label method),
(unit factor method)
t (dimensional analysis) t
t

t
12.11 3 (inch) cm
18.0
1.012
31.122
t 1 inch = 2.54 cm
18.0







t
t
t t
P
t


t



(rounding off)
P t


t 5
t tP

t
t t



t
t

t
t t
t t

t
r
t t t 2L m3
t t

t
t t 1L = 1000 cm3
 11

m3










P


t

(s)

(day) = 24 (h)


q rs t

r



t




+
2g 16 g 18 g


+

2g 32 g 34 g
16 g 32 g

(2g)


16:32 1:2
12

q
P s q
s q q
q
q
100 mL 50 mL
100 mL t q
+ q q
100 mL 50 mL 100 mL
Journal de Physidue
100 mL 50 mL
2:1 50 tr 1860
qr t
s

q



q
1811
(atomos)
q s

q

q s
(460-370 BC)






s

P
(A New System of Chemical Philosophy)

s

 13

amu



=

= 1.0078 u
= 1.0080 u

s 16(16O)

15.995 amu

amu u s

(unified mass)

s


P
s t

r s



r




(%) (u)

98.892 12

1.108 13.00335
q r s t
2 10 10
14.00317
t

s s
r


= (0.98892) (12 u) + (0.01108) (13.00335 u)

+ (2 1010) (14.003.17 u) = 12.011 u
12 (atomic mass
s
unit-amu)

r




t

1 amu = 1.66056 1024g
s
= 1.6736 1024g
14

1.10

NaCl


= (12.011u) + 4 (1.008 u) = 16.043 u
= =
2 + 1
+
= 23.0 u + 35.5 u = 58.5 u

= 2 (1.008 u) + 16 u = 18.02 u qrst t

Score, 144
= (gross)
6 (12.011u) + 12 (1.008 u) + 6 (16.00 u)
= (72.066 u) + 12.096 u) + (96.00 u)
= 180.162 u
SI mol
P



12 12g 0.012
kg


12

1.992648 1023g
12 g




Na+ Cl

 15

6 022 136 700 00 00 00 00 00 00 00





= 6.022 1023
= 6.022 1023
=

6.022 1023
1.11

= 18.02 g

P




qrs t r
r r r




= 18.02 g mol-1

= 58.5 g mol-1





ts qrs qr tq qq t
t t r r
16

H : C : Cl s 2 : 1 : 1
4.07% 24.27% q
71.65% 98.96
g s s






r 100 g r

s
100 g 4.07 g 24.27 g q
71.65 g
s

r s s


s

q s


s n

t n = 2
2.021 q r 2.021 r

t q r
s
s



s
s
s
PP



(stricheion),
(metron), q
 17

2
g
(s) (l)












P
s s
s s
q
r
t
r

q
r
r

q q q
C C


H r H H
H
q q q
O

q q q
r


(subscript) r
18

qr
qr

qr q qr
qr


q (limiting reagent)
qr
qr t

0.5
16 g (g) 0.5



50.00 kg N2(g) 10.00 kg H2(g) NH3(g)

(i) NH3(g)
(ii)
2 NH3 qr
2 t

1
qr

s
2

N2(g)
s







P P




qr

H2(g)

17.86 102 H2(g)

= 17.86 10 2
 19

ts
ts
ts
3
3
= 5.36 10 H2(g) 3.30 10 NH3(g)
4.96 103 H2(g) (g)
H2(g) NH3 (g) = 17.0 g NH3 (g)
NH3(g) H2(g)
3
3.30 10
3
4.96 10 ) s
H2(g) 2 NH3(g)
4.96 103

A 2g 18g
P (A) P


P (w/w%)

A P =






M
s qrt
1L
qrt



(M) =



A B
NaOH 1M 0.2 M
nA nB


1 M NaOH 1L 1
A
NaOH 0.2 M IL


NaOH
M1 V1= M2 V2
B M V M1=0.2;
20

V1=1000 mL r M2=1.0;


V2 r r

.2 M 1000 mL = 1.0 M V2





1 L 0.2 NaOH

r 0.2 NaOH
r 1L r r
(1M) NaOH r r r r r r
0.2 NaOH r
r r
1 L 1000 mL r 1 r 3 M NaCl l.25 g ml
1

r 0.2 r r

m = 3 mol L
1

r 1 M NaOH 200 mL r 1 L NaCl = 3 58.5
r r r 1L = 175.5 g
200 mL (NaOH) 1 L = 1000 1.25gm
0.2 r (1000 mL)
= 1000 1.25 = 1250 g = 1250 gm
r r (0.2)
rr NaOH = 1.25 g mL1
= 1250 175.5

= 1074.5 g
1 kg P
m qst qt s
t t

r r r t qs
qst qt s
t t
r r
qs t


NaOH r
r r
4 g NaOH r
r r
r r
250 mL r
r r
(Stock solution) r

r r


r rr r r

r r
 21

r PP P


t


SI

1031 1023
P r PP P
qs PP


sP PP
P s P Pr P s Pr Pr P s P qs PsrP P s
PPPP P s P P PP P r
t PP sP 12C u


PPsPP
P P

PP PP PP (6.022 1023)


rr PPs
t
t PsPqq t



22

(i) H2O (ii) CO2 (iii) CH4
(Na2SO4)
69.9%
30.1%

(i)
(ii) 16 g
(CH3COONa) 500 mL, 0.375
82.0245 g mol1

69% 1.41 g mL1
100 g (CuSO4)

g g

% P
35
Cl 75.77 34.9 689
37
Cl 24.23 36.9659
(C2H6)
(i)
(ii)
(iii)
20g (C12 H22 O11) 2L

0.793 kg L1 0.25 M 2.5 L

SI

1 Pa = 1 Nm2
1034 g cm2
SI

q
(i) 106
(ii) 109
(iii) 106
(iv) 1015
(v) 10
 23

15 ppm
(i)
(ii) t t

(i) 0.0048 (ii) 234,000 (iii) 8008
(iv) 500.0 (v) 6.0012
t
(i) 0.0025 (ii) 208 (iii) 5005 (iv) 126,000
(v) 500.00 (vi) 2.0034
t t
(i) 34.216 (ii) 10.4107 (iii) 0.04597 (iv) 2808
t t

t
(i) 14 g 16 g
(ii) 14 g 32 g
(iii) 28 g 32 g
(iv) 28 g 80 g
P

(i) 1 km = ........... mm = ............ pm
(ii) 1 mg = ........... kg = ............ ng
(iii) 1 mL = ........... L = ............ dm3
3.00 108 m s 1 2.00 ns t t
t t
t
(i) A 300 P + B 200 P
(ii) A + 3 B
(iii) A 100 P + B 100 P
(iv) A 5 + B 2.5
(v) A 2.5 + B 5

t P t

(i) 2.00 103 g 1.00 103 g t
t
(ii)
(iii)
24

0.5 mol Na2CO3 0.50 M Na2CO3

r
r r
(i) 28.7 pm (ii) 15.15 pm (iii) 25365 mg
r
(i) 1 g Au (s)
(ii) 1 g Na (s)
(iii) 1 g Li (s)
(iv) 1 g Cl2 (g)
r r r r r r 0.040
r r
12C (g)
r r

(i)

(ii) P
(iii) 0.0125 + 0.7864 + 0.0215
r r r r r

q
Ar
36
35.96755 mol1 0.337%
38
Ar 37.96272 g mol1 0.063%
40
Ar 39.9624 g mol1 99.600%
r
(i) 52 r Ar (ii) 52 u He (iii) 52 g He
r
r 3.38 g 0.690 g r
10.0L STP 11.69 g
(i) r
(ii)
(iii)
CaCO3 r HCl r CaCl2 CO2
s t s s
0.75M HCl 25 mL r CaCO3

r r (MnO2) r HCl r
r
s t s s
HCl

qrs
STRUCTURE OF ATOM

ttt ttttt ttt

(400 )

P
(atom) atomio

(uncutable)


(non-divisible)

(i)

(ii)

26

(iii)
r
(iv)
r r


qst qst





(ebonite)
(fur)


r

r

PP
(TV


r
r
(deposition)







(i) (cathode rays)



(ii)


qst




 27

(iii) (iii)

t rs

(iv) rs

(v)

P



e/me




= 1.758820 1011 C kg1 (2.1)

(e) (me)

me
kg

(C)

e
(i)
P
q rs

(ii) t

28

P
atomizer qs tq q
condenser t t qs q
q t t qs s
tt
(i) qs t qs
r
qs tq q t
X-
q s t t

(ii) qs t q t

X- t q t
(iii) t qs q q
sq
(iv) q t qs q
t qs

(q) q t t t
(e) q t qs q
q = ne n = 1, 2, 3... qs s q t
s q t qs q q
qs q t q t
qs q t
q t qs t t t
qs q q t qs s s s


s
q t s tq
sq s (sub-atomic) qs
'e'

t s s q qt





t s q

t qs q t
q q t t t
t q t 1.6 1019 C,
q q
q tt t 1019C t

e/me t t t s q q P
t q t (me) t q t t t q q s q

t 1010m
t t

t q q

= 9.10941031 kg (2.2) q t
 29

(plum P P P

pudding)] (raisin pudding) X- P

(watermelon)
qr s tq q sP

qr q X-
X- qP P q P
P

(deflect) P q r P
P (penetrating power) P

qP qr P s

P Ps

(wavelength) P P (0.1 nm)

q P

q P

qr Henri Becqueral 1852 1908

qr Pq q q P

t (radioactivity)
P P Pq

P r

P qP P

r s

q q

P

P qr

P
q q r s q
qr q q P
q (Wilhem X- qr q P
Roentgen, 1845-1923) P P
q r P P P
P q r qr s
q r PP (fluorescent) P s
PP P s P
30

(gold foil) P
P
P
100 nm P P
P P
P
(fluorescent) (i) P
P
(flash) (ii)

(iii) 1)
180


(i)

(ii)

t (repulsive
force)


P

(iii)

q 1010 m
q 1015 m


P q
5 km
t P P



(shot) (i) P

rs
 31

(ii)

(orbit) (Z)
(A)

(iii)



%

s t

t



tt (Tritium,31T)
P




(Z)

Z








(Z) = q r


s tr r

= r

t r

t (n)



, Z = 35, A = 80,
nucleons

=
= Z = 35
r s t r (Z)+
= 80 35 = 45

t r (n)

(X)

(A)

(Z) = 16

(S)
32

= (accel-
eration) t
+

= 16 + 16 = 32
t
t
qs t
qs t
= (18 16 = 2) t



(orbit)
P t
(spiral) t 108s

t qs t
= =



P

A Z t
t
t q

t
P

t t
t (kq1q2/r2) P s t
q1 q2 r t q
k

m1
r
m2 r t
G t
* t
t t t t


t
t t (i) qs t

*

 33

P
P

(ii)
(ii) P

(iii)
P

t P

P
P

P
(radiofre-
P P quency) 106 Hz

(waves) (microwave)
q
rs q
rs r 10 Hz
2

(infrared) 1013Hz

(ultraviolet) 1016 Hz

1015
corpuscles Hz (visible)

(iv) P

() ()

() SI

P P (Hz,s ) 1

(m)
P

P



P
(i) P P

3.0 108 m s1 (2.997925 108 m s1)

34

(speed of light) q
c ( ) ( )


(c) q

s q
c=
r r

( )
(wave number)
(400 nm)
m1
(750 nm)
cm1 SI 9
(Hz) r (1nm = 10 m)
P

1,368 KHz
(transmitter)

r
14
= 7.50 10 Hz

c

14
= 4.00 10 Hz
t c
r r
4.0 1014

7.0 1014 Hz

 35

(iv)

5800 A r

r r

r
r ( ) r r

r r r r

r


r r r

r r r r

r r r


r r r

r r r

r r

r r r

( )

r
P
s P r r r r
s
P
(black body) r r

r r

qt q qt qt
(exact) r rr
q q r r

r* (diffraction) r r ** (interference) r r rr r

r r r r

r r r r r

r r r

r r r r r
r r r

r r
r r
r

r
(discrete) r r r
(i)
r r
black body radiation)
r
r

(ii) r r r

r (quantum)

(iii) r r (E) ( ) r r

r r r

E = h

**

36

(i) s q
ts
q s q
sq (time lag) s
(ii) s s

r rr

r

r r r r
(1858-1947)
r r
r r r
r r
(iii)
P t (threshold frequency)
s q q
(Institute of theoretical Physics) s > 0 q s




q q qs qsq
P
s q q s s qt
qst ht q q
q 6.6261034 Js q q q s ts s s
s qt s q ss
s q q q
qs s q s s q q q t
s q q s q
q t q
s t
qs [ = (4.3 4.6) 1014 Hz]
s s
t t t
ss t s
q q
s t qs qs
s t s = 5.1 5.2 1014 Hz q t
q s
q q s ( 0) 5.01014 Hz
 37

(1879-1955)
t P P

P P P

t P P

t P

PP P
P q r Ps

q s P P P

P q Ps P

P
P P r

5 1014 Hz



h

h0
W0 (h h 0)
(E)


(conservation of energy)

E =h
34
h = 6.626 10 J s
14 1
= 510 s ( )
(2.7)
34 14 1
E = (6.626 10 J s) (5 10 s )
me 19
= 3.313 10 J

Li Na K Mg Cu Ag

W0 /eV 2.42 2.3 2.25 3.7 4.8 4.3

38

= (3.313 1019 J) (6.022 1023 mol1) 5

= 2.31 10 J mol
1

1
= 199.51 kJ mol s r


400 nm

= 100 = 100 Js1

= E = h = hc/
P
= 517nm



P
0, 7.0 1014 s1

=1.0 1015 s1
q s

300 nm r r
q 1.68 105 J mol1 = mev2=h( 0 )
s r = (6.626 1034 J s)
s t r r (1.0 1015 s1 7.0 1014 s1)
s = (6.626 1034 J s)
(10.0 1014 s1 7.0 1014 s1)
r
= (6.626 1034 J s) (3.0 1014 s1)
= 1.988 1019 J
300 nm (E)
*



rr
= 6.626 10 J
-19
rr
r r r
= 6.626 10
19
J 6.022 10
23 1
mol (refract)
5 1 r r
= 3.99 10 J mol
r
r r s t r q
r r r
5 1
= (3.99 1.68) 10 J mol
* discreat
 39

(spectrum) P

7.50 1014Hz

4 1014Hz
r
(continuous spectrum)
r

r

r
r

(spectroscopy) r

q st q

q q qqqq
(slit)

40

P (Balmer
series)
t

r

s P



(2.9)

n1=1,2........ n2 = n1 + 1, n1 + 2......
109,677 cm1
(Rydberg constant) n1 = 1, 2, 3, 4

(Lyman), (Balmer), (Pashen),

(Bracket) (Fund)

r


(Rb), (Cs), (Tl),

(In), (Ga), (Sc)

(He)
P

t
H2
t


r
(i)
(ii)
( ) q
s P


(2.8)


n = 3, 4, 5 ...
 41

(i) P

(ii)

r r

t s

(m) (v)

(angular

momentum) (I) ()
me

(r)




=I


I = m er 2
= v/r v

P
= m er 2
v/r = mevr
q r s tt
(iii) E


r

(2.10)

E1 E2

(iv)

n = 1,2,3..... (2.11)

'Atoms for Peace'

h/2

r


42

n =



En
n = 1,2,3...

(principal quantum number)

(rest)



rn = n2 a0 (2.12)
n = E= 0
t a 0 = 52.9 pm
52.9 pm n En
(n = 1) n
n r = 1

P



t n = 1,2,3.... (2.13)
He+ Li2+, Be3+
t RH (Rydberg constant)
2.18 1018J t
(ground state)

E1 = 2.18 1018 ( ) = 2.18 1018 J (2.14)

n = 2 E2 = 2.18

1018J ( )= 0.545 1018 J.
r (2.15)

t Z



Z

t

n =
qr sq
n t


 43

ni > nf E

ii
P q

r r

s


P
s q




E = Ef Ei (2.16)

q ni r nf st

n=5 r n=2 r

s

(2.17)


(2.18)
ni = 5 n f = 2
r

t s

(2.18)










(2.19)

(2.20)












s


14

= 6.9110 Hz
(2.21)

nf > ni

q r
44

He
+

1

atom
+
He n = 1, Z = 2




P

r


n = 1 Z = 2


r



q st t t



He+, Li2+, Be3+
t t

P


(i)

[ (doublet),

]



( ) (p)

(2.22)

m v p

(ii)

 45

t


t

t


t


t

t


t

t t t

t 3.6 A t

t t

t

t




1
=
0.1 kg t 10 ms

29
= 6.135 10 kg

P

P P

34 2 2 t
= 6.626 10 m (J = kg m s )

t t

9.1 10
25
kg t
t t

25
3.0 10 J t

t
(2.23)

t

=


x p
t

(p )
x

x
q
r
t

s
t

x
t t






v )

v
x

t t

x
x



46

(106 kg)


r q
st


q t
ss

v.x





9.11 1031kg












P

108m
(trajecto-
v
ries)
















r
 47

s
s

t

18
10 t t


P

0.1 t

t t

qr

t t

t


t



7 1 2 2
= 0.57910 m s (1J = 1 kg m s )

6 1
= 5.7910 m s

40g 45m/s
t
2% t

t
t


t t

t t
2%

t t







(quantum machanics)

48

st t t
t
r r t t t
r tt
r r t
r r
r tt

r r r r
t t
r
t
r r r t t
r r r r r t
r r r t
t t
rr r t t
r r r r
r r ber)
ml (magnetic quan-
r r tum number)] r r
r r r r
r r r r
r r

r
r r
r r
r r r
r r
r
= E r r
r (operator) (atomic orbitals) r
r r
r r r
r
r
r r
r
r r

(predict) r r
r E
r r r
P
r
r r r r r r r
r r r r q
r () r r r (exact)
r r rr q
r r r r
[ n (principal quantum num- r r r
ber) l (azimuthal quantum num- r
 49

r


r s s


2
r P
n l
(probability density)



n
2

P




qr st

s s

qr s

s

s



n, l ml

r 'n',

(probability)

s s

He , Li2+
+

s



(shell)

t

s
n

'n2'

s n

n = 1 2 3 4 ............

= K L M N ............

s

s
n


50

r n st s s
s (n = 1) st s l
= 0 t st s (n = 2)
(l = 0, 1) n = 3 t (l = 0, 1, 2)
st s n r t
s q r (l )
t t s l t

rt t s

l


(n, l, ml )
t (notation) s p d f g h ......
r q r l
t t s
2

2

2
2



2



2

P 'l'
(orbital angular momentum) q r
(subsidiary quantum number) st s s
t t s n (magnetic or-
l 0 n 1 t n s t s bital quantum number) ml t
t n l 0,1, 2,....(n 1) t s
s t s ml 2l + 1 s
s n = 1 st s t l t s
0 st s n = 2 l 0 t ml = l, (l 1), (l 2) .... 0, 1 .... (l 2), (l 1), l
s t s n = 2 l 0,1 s t ml s t
(sub- st s t 2(0) + 1 = 1 s t s
shells) t (sub-levels) st s r ml=1,0,+1 s t s [2[1]+1=3p
 51

] ml = 2, 1, 0, + 1 + 2

d ml t

(i) n

ml t

(ii) nth n r
l

nl = 2,l = 1, ml = 0 r

t t (2l +1) r

r s (l = 0) p (l = 1) 5d
t (l = 2) l t r

l 0 1 2 3 4 5

r s p d f g h

1 3 5 7 9 11 (iii) ml t l

t ml (2l + 1)


r





r
t r
(iv) ms
t

r q ( r P

(n = 3)
r
s (George Uhlenback)

(Samuel Goudsmit)

t n=3 l 0, 1 2

r (ms) 3s n =3,
l =0 ml = 0 3p

(n = 3, l = 1 ml = 1,0, + 1)
t t

3d
(intrinsic)

n = 3, l = 2 ml = 2,1,0, + 1, + 2
t (vector)

t 2 2
=1 + 3 + 5 = 9 = n 3
ms t
=9
ms + 1/2 1/2

t (spin states)
spin up) P
spin down t
s,p,d,f
ms t +1/2 t

1/2 t

t
n 2, l 1 n 4, l 0,
n 5, l 3, n 3, l 2
52

t t t 2s
n l t
2 1 2p t
t r
P (small maxima)
4 0 4s
t
5 3 5f
t
3 2 3d ns (n 1)
n
t 2s

3s


(coordinates)
t
r (dots)
[
1s (n = 1, l = 0) 2s (n = 2, l = 0)
]

1s r 2s q r
q r r
qrs q
1s r 2s r r 1s r 2s r q
r r q q q

t
(boundary sur-

face diagrams) t
[

1s 2s r
(contour surface)


1s 2s t t t
1s P
 53

90%
1s 2s 4p > 3p > 2p s


n 2 t
100%
q

100%
s

90%

1s 2s

n s

t 4s > 3s > 2s > 1s

s 2p

l=2 d

(lobes) (n) l n

1 ml

2, 1, 0 + 1 +2 d

d dx y , dyz, dxz, dx2y2 dz2

d

dz2

n > 3 d

(4d, 5d, ---

2 2
*r r r r

54

PP P
r
r


1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p
= 4d = 4f < ........... (2.24)
r qs t
t r
r
(degenerate)
r

(ground state) r
r
2s, 2p
r
r (excited state)

3d

np nd

pz xy
dxy z-
xy r


l
p d
r
(n 1) l
(nl1)
 55

(l )

Zeff p s

s, p, d, f ... d p

p s

d p

(splitting)

n l

n l

n l

(n + l )

(Ze)

(n + l ) n

(n + l )

(Ze)

(shielding)

P
Zeffe (Zeff)

(effective nuclear charge)

2s
2s

(Z) E2s(H) > E2s(Li) > E2s(Na) > E2s(K).

qrsrt q rr r rr rr







(Pauli's exclusion principle),
s p
(Hund's maximum multiplicity rule)


p
d

p
p
d
56

r r
r
(n + l)

P
q s t t r
q s t r
q s s t s n,l s
t ml s t
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d, q
6p, 7s... s
s qs
s t 1s q s
s t s s
t 1s s
q s t
s t p s d s

s s t q
q s t
s s s t n
t s 2n2 r
r


r s q
s s t P s t q s
 57

(degenerate orbitals)

(Li) P


1s

2s
p d f
P 1s 2s 2 1

p, d f
2s P
P
1s2 2s2

P

2p
qr s tqs
P
P
P (B, 1s22s22p1),
(electronic configuration)

P
(C, 1s22s22p2),
(N, 1s22s22p3),
P P (O, 1s22s22p4),
(F, 1s22s22p5),
P P (Ne, 1s22s22p6).

2p P
(i) sa pb dc

(ii)

s p d

a, b, c

P P

1s
Na, 1s22s22p63s1) P (Ar,1s2
P 1s1
2s2 2p6 3s2 3p6)
1s
P Li Ne
P (He) P 1s
3s
P

1s2 P
3p

P P (Ne)
P
58

6p, 7s 5 f
(Na, [Ne]3s1), (Ar, [Ne] 3s23p6) 6d (U)
r t
t
t
Ne Na Ar
(K) r (Ca) 3d
4s t
r 4s
t
3d 4p r
He r Ar
(Sc), (Ti), (V),
(Cr), (Mn), (Fe), (Co), t
(Ni), (Cu) r (Zn) 3d
t
r 3d r

P P
r r t p3 p6, d5,
d10, f7, f14 r r t
r r r
d5 d10 r
Cu r Cr
3d (Ga) 4p t 4s r 3d
(Kr) t s
(Rb) (Xe) t r
5s, 4d r 5p r t t
4s, 3d 4p r 6s Cr r Cu
(Cs) r (Ba) 3d5, 4s1 r 3d10,
t 4s1 3d4, 4s2 r 3d9, 4s2
r (La) (Hg) 4f 5d r
 59

3d
P

P (exchange
energy)

(half filled) qrs

t t

t t

(i) t (ii)

(iii)

5
t t t
d
60

*
 61

**
62

-













P


P

P


r n, l, ml






r He , Li
+ 2+


n l
(n + l )
(n + l ) n
 63

(i)

(ii)

(i)

14
(ii) 7 mg C

= 1.675 1027 kg

(iii) (STP) 34 mg NH3

(A) (Z)

(i) Z = 17 , A = 35.
(ii) Z = 92 , A = 233.
(iii) Z = 4 , A = 9.

() 580 nm ()

(i) 3 1015 Hz

(ii) 0.50
10
2.0 10 s

q 4000 pm 1J
7
r 4 10 m 2.13 eV

(i) eV (ii) (iii)

(1 eV= 1.6020 1019 J)

s 242 nm t


1
kJ mol

s m

6800

(0 ) (W0 )
64

t t n = 4 t n = 2 t t
r t r
n = 5 H t
r t t
n = 1 t
t t t n = 6 t t
r
(i) t t 2.18 1018 J atom1
t
(ii) t r t
t r r r
t
t t t
t r t t r
t r t 2.18 1011 ergs
t t En = (2.18 1018)/n2 J t
n = 2 t r t
r cm r t r t
2.05 107 m s1 r r r r
9.1 10 kg rt t 3.0 1025 J
31

r r t

Na+, K+, Mg2+, Ca2+, S2-, Ar
(i)
() H () Na+ (r) O2 () F
(ii) t
t
() 3s1 () 2p3 (r) 3p5 ?
(iii)
() [He] 2s () [Ne] 3s 3p (r ) [Ar] 4s 3d .
1 2 3 2 1

n g r
3d n, l ml t
(i)
(ii)
H2+, H2 O+2
(i) n = 3 l 2ml r
(ii) 3d ml l
(iii)
1p, 2s, 2p 3f
 65

s,p,d

n = 1, l = 0
n = 3; l = 1
n = 4; l = 2
n = 4; l = 3

n = 0, l = 0, ml = 0, ms = +
n = 1, l = 0, ml = 0, ms =
n = 1, l = 1, ml = 0, ms = +
n = 2, l = 1, ml = 0, ms =
n = 3, l = 3, ml = 3, ms = +
n = 3, l = 1, ml = 0, ms = +

n = 4, ms = n = 3, l = 0

He+ n=4 n=2

He+ (g) He2+ (g) + e

2.18 1018 J atom1

0.15 nm

20 cm
8
2 10 2.4 cm

P 2.6 1.6 cm

2.5 1016C

1.282 1018C

79
Br


35
Br

31.7%

11.1%
66

%


(oven)
(amber)


X-

337.1 nm
5.6 1024
616 nm


2J

600 nm
3.15 1018J

2ns
2.5 1015
589 589.6nm

1.9 eV

500nm




P (nm) 500 450 400
5 1
v 10 (cm s ) 2.55 4.35 5.35

0.35V
256.7 nm
150pm
1.5 107ms1
n n = 3 v = 3.29
1015 (Hz) [ 1/32 1/n2] 1285 nm

1.3225 nm 211.6
pm
 67

s s ss s s
s s s

s s s s s s s

s 1.6 106 ms1 s s

s s

s s s s s s

800pm s
s s

s s s s
s 2.9 106ms1 s s s

s s 1000 V s s s s 4.37 105 ms1 0.1 kg

s s s s s

s s 0.002nm s s s
s s s

s s h/4m 0.05 nm s s s s s

s s s s s s s s

1. n = 4, l = 2, ml = 2 , ms = 1/2
2. n = 3, l = 2, ml = 1 , ms = +1/2
3. n = 4, l = 1, ml = 0 , ms = +1/2
4. n = 3, l = 2, ml = 2 , ms = 1/2
5. n = 3, l = 1, ml = 1 , ms = +1/2
6. n = 4, l = 1, ml = 0 , ms = +1/2
P s s P s ss s 2p s s 3p s s
4p
s s ss s s s s

s s s s

(i) 2s 3s, (ii) 4d 4f (iii) 3d 3p.

Al Si s 3p ss s s
s s

s s

ss P Si Cr Fe Kr
n=4 s s s

s s
s s s s s



CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES

PsPPP P PPP P PPPPPP P P P q

q PPPs P P sPP PPP PPPPPP PP PP PP PsPP
t
sP Pq P PPP PP P sPPPPPP PPP P
r P PP P q

r



r



r
IUPAC
s, p, d f

r

r



t r r r






r
t r








r rr
69

qssssq qssssq qssssq

Li 7 Ca 40 Cl 35.5
Na 23 Sr 88 Br 80
K 39 Ba 137 I 127

t t

Ca

t
t
P t


(A.E.B. de Chancourtois)
t t


P
P
(curve plotting) t
t


t
t
t
t (Law of

octaves)
P

t (eight musical note)

Li Be B C N O F
qssssq 7 9 11 12 14 16 19
Na Mg Al Si P S Cl
qssssq 23 24 27 29 31 32 35.5
K Ca
qssssq 39 40
70

(Germanium)


r (Eka-Aluminium)
(Eka-Silicon)

r








P

(empirical formula)
r qsqt q qq q
qq q q
r

r

VI VII
X-
X- r Z
r P

P
r
(Gallium)

68 70 72 72.6

/ (g/cm3) 5.9 5.94 5.5 5.36

/K 302.93 1231

E2O3 Ga2O3 EO2 GeO2

ECl3 GaCl3 ECl4 GeCl4

r rr
71

72

Tobalask

(Master's)
r
'Principles
of chemistry'


P


(1834-1907)



(observed)


r

(Ramsay) r (Krypton) r (Xenon)


(Accurate barometer)




(Mendeleevium)
(Glenn T. Seaborg)
P
P
P (Transuranic
Elements)
r rr
73

P n

t t t P

(The physi-

cal and chemical properties of the elements are P

periodic functions of their atomic numbers.)

P
*

P P
P

P (International Union of
P Pure and Applied Chemistry)

q s

P P

t P

P t P

q (Rutherfordium)

(periods) (Kurchatovium)
(group)
P IUPAC s P
t IUPAC t
t IA...VIIA, VIII, (numerical
IB...VII B,
root)

*

(Sg)
74

IUPAC



r

I AVIIA, VIII, I BVII B

r








r













r


r
r






r


r
r

r


r rr
75

IUPAC

q s

0 nil n
1 un u
2 bi b

3 tri t
4 quad q

5 pent p
6 hex h
7 sept s P
8 oct o
IUPAC
9 enn e
(symbol)


(ium) t

IUPAC
(root) un, bi nil

Unbinilum

IUPAC Ubn

q s q IUPAC s IUPAC s

101 Unnilunium Unu Mendelevium Md

102 Unnilbium Unb Nobelium No
103 Unniltrium Unt Lawrencium Lr
104 Unnilquadium Unq Rutherfordium Rf
105 Unnilpentium Unp Dubnium Db
106 Unnilhexium Unh Seaborgium Sg
107 Unnilseptium Uns Bohrium Bh
108 Unniloctium Uno Hassium Hs
109 Unnilennium Une Meitnerium Mt
110 Ununnilium Uun Darmstadtium Ds
111 Unununnium Uuu Rontgenium* Rg*
112 Ununbium Uub * *
113 Ununtrium Uut +
114 Ununquadium Uuq * *
115 Ununpentium Uup +
116 Ununhexium Uuh * *
117 Ununseptium Uus +
118 Ununoctium Uuo +

* IUPAC +
76

r r (n = 4) 4s
r P q 4p
q 3d
(energetically) q
(n) 3d
(shell)
(3d transtitian series)

(Scandium : Z = 21)
s, p, d, f
3d1 4s2 3d

q

4p

(Krypton)

P P P
4d

(ytrrium, Z=39) 4d (4d transition
P n P
series) 5p
(successive
period) qs t n=1, n=2 (Xenon)
P 6s, 4f, 5d 6p
4f
(cerium, Z=58) q (Lutetium,
(n=1) P (1s) Z=71) 4f

(Lenthanoid Series)
(1s1) (1s2)
(n=7)
K q q
(Li=1s2,2s1) 2s 7s, 5f, 6d 7p
P (artificial methods)
(1s2,2s2)
P P P q
q P
L
(Actinium, Z = 89) 5f
q q
5f

(5f inner transition series)
3s
3s 3p (Actinoid Series) 4f 5f
P

r rr
77

s,p,d f
t

t
t n=5 l=0,1,2,3

4d, 5s 5P t
(valance shell)
5s<4d<5d
(He=1s ),2





s- (H=1s1)

P



t






t
ns1


t

t


t

qs

s,p,d, f

t s

(Aufbau Principle)
(vertical columns) t

(Group) (family) ns1 ns2

s t

3 Li 1s22s1 [He]2s1
11 Na 1s22s22p63s1 [Ne]3s1
19 K 1s22s22p63s23p64s1 [Ar]4s1
37 Rb 1s22s22p63s23p63d104s24p65s1 [Kr]5s1
55 Cs 1s22s22p63s23p63d104s24p64d105s25p66s1 [Xe]6s1
87 Fr [Rn]7s1
78

r rr
79

10 2

d-

s-

s d-

f- P P
p- P P
P
p-

p- s-

(Representa- (58Ce 72
Lu)

tive elements) (Main Group (90Th 103

Lr)

Elements) [(n2)f 1
ns2, np 1 ns2, np 6
14
(n1)d 01
ns ] 2

ns2 , np6
f

f-

s ts

s s

q

(Halogens)
(Radioactive)
(Chalcogen)
(Nenogram)

(negative

electron gain enthalpy)
q q

s
q

d- P P P

s

d
At
14 10 2 5

110

02
[Rn] 5f 6d 7s 7p
s

Ra
2
Zn, Cd [Uuo] 8s
80

r s-,p-,d r f- r r
r r r r r r r r
r r r r r r
rr r r r r r
r r r r
r r
r [
r r r
r 303K 302K ] r
r r t r
r r r r
r r r
r r r
r t
r r r
r r t r r r r r
r r r rr
P r r
r r r
r r r r rr
r r r
r r r r r
(Brittle) r r r r

r r
(abrupt) r r r r

(Zig-Zag line) r r
r r r r r
r r (Ionization Enthalpy),
r r r (Electron Gain Enthalpy)
r r (Metalloid) r r (Electronegativity) r P

r r
r r r r r
r r
Si, Be, Mg, Na P
t r r
r ( 1.21010m) r
r (electron cloud)
r P r r r r r
r r r r t
r r r

qs r t
r rr
81

(Single Bond)

(covalent molecules) P

(covalent

Radius)

(bond length) P

pm

pm

(Metalic Radius)

(Internuclear

distance)
(n)
pm
(valence electron)
pm pm


P
(Atomic Radius)



x-
P




P

q st s t s ts (pm)

II Li Be B C N O F

152 111 88 77 74 66 64

III Na Mg Al Si P S Cl

186 160 143 117 110 104 99

q st s s ts

I 17

Li 152 F 64
Na 186 Cl 99
K 231 Br 114
Rb 244 I 133

Cs 262 At 140
82

qs t qs t

(parent atom) PP




2+ 3+
Mg, Mg ,Al, Al




(F ) 136 pm

pm

pm Na+

95 pm


Mg
(Isoelectronic 3+
Al
species)
O ,F ,Na ,Mg ,O
2 + 2+ 2

r
r rr
83

(Ground State)
(Isolated Gaseous Atom)

(X)

X(g) X+(g) + e (3.1)

(kJ mol1)

. 3.5 qs


(i)
+ 2+
X (g) X (g) + e (3.2) (ii)

(core elctrons)

(shielded)

(Screened)

(shielding Effect) (Screening

Effect)

(Specified) (Effective Nuclear charge)

(Actual Nuclear charge)

P 2s

1s

(curve)

(maxima)

(closed electron shell)

(Minima)

ns1 n
=

(Inner Core Electrons)

P
(compen-
84

Fig. 3.6 qrs
qrs

sate) 2p
2s
(Shielded)
2s
2p
t


t

2p
p
t
t 2p 2p

2p
t (Z = 5) 2p
(Z = 4) t 2p
t


t s p
Na, Mg Si
s P
k J mol1
p kJ mol1
2s (penetration) 2p t
r rr
85

qs t

1 t
k J mol

3p
3s

P

t P (X)
P
P t s
P (anion)
s P



P P
t
t
P
P
P
tqs
P P


s


X(g) + e X (g) (3.3) P t P

P
P s

(exothermic) (endothermic) P

t P

P t P t

P P

t
P P

P P t t P

P P

t (n = 2)

t
P

n = 3 S Cl

* (kJ mol1)

1 eg H 16 eg H 17 eg H 0 eg H

H 73 He + 48
Li 60 O 141 F 328 Ne + 116
Na 53 S 200 Cl 349 Ar + 96
K 48 Se 195 Br 325 Kr + 96
Rb 47 Te 190 I 295 Xe + 77
Cs 46 Po 174 At 270 Rn + 68

* (Electron Affinity) (Ae )

86

(space)



Li F
P,S,Cl F
F At






3p

2p





P

q












r




st

r rr
87

( II) Li Be B C N O F

1.0 1.5 2.0 2.5 3.0 3.5 4.0

( III) Na Mg Al Si P S Cl

0.9 1.2 1.5 1.8 2.1 2.5 3.0

( I) ( 17)

Li 1.0 F 4.0
Na 0.9 Cl 3.0
K 0.8 Br 2.8
Rb 0.8 I 2.5
Cs 0.7 At 2.2

OF2 Na2O

F>O>Na
2s22p5

P
P


P

(diagonal relationship),
-1
(Inert pair effect), P (effect of 2s 2 2p 4

lanthanoid contraction)

+2

Li F P

q st

1
3s
P
+1

P
P
(Representative Elements)
P
P

P

(Periodic Trend)

P
88

1 2 13 14 15 16 17 18

1 2 3 4 5 6 7 8

1 2 3 4 3,5 2,6 1,7 0,8

(Variable q r
Valency) r
r r s
r
r


t

(prediction) (Diagonal Relationship)

r
r
r


2s 2p
t
(3s, 3p, 3d)

[BF4] r

P
[AlF6]3

1 2 13 14 15 16 17
LiH B2H6 CH4 NH3 H2O HF
NaH CaH2 AlH3 SiH4 PH3 H2S HCl
KH GeH4 AsH3 H2Se HBr
SnH4 SbH3 H2Te HI

Li2O MgO B2O3 CO2 N2O3, N2O5

Na2O CaO Al2O3 SiO2 P4O6, P4O10 SO3 Cl2 O7
K2O SrO Ga2O3 GeO2 As2O3, As2O5 SeO3
BaO In2O3 SnO2 Sb2O3, Sb2O5 TeO3
PbO2 Bi2O3
r rr
89

M/ pm Li Be B

152 111 88

Na Mg Al

186 160 143

Li Be
n+
M / pm 76 31

Na Mg t

102 72

p p
t qs

(t C = C, C C, N = N, N

C = N, C N), t t

qs

t t

2+ t t
Al [Cl(H2O)5]


(oxidation
t

state) t


Na2O t
+3 t

6
Cl2O7

Al2O3, As2O3
P

P
CO, NO, N2O (amphoteric)

t
t
t

t

t Na2O
Cl2O7

t
t t
Na2O t

t Cl2O7
qs
2Na + H2O 2NaOH
s t
Cl2O7 + H2O 2HClO4
t

90

3d

4f s-

P
P P
q rs t q
q P r (Valence Shell)
q r P
s (Valencies) P
P q s- t p- t d- f-
1s P r
r t r
t P t (Semi metals) (Metaloids)
Si, Ge, As q P q
q P q P P

P t t t
q
s q

q P
P
r P
r q q
P r s q P
P t P
t
r rr
91

Z=14

(i) P

(ii)

(i) F (ii) Ar (iii) Mg2+ (iv) Rb+

N3, O2, F, Na+, Mg2+ & Al3+

P
P

2.18 1018J

P J mol 1

P Li< B<Be<C<O<N<F<Ne

(i) Be i H , B

(i) O i H , N F

P P

P

92

(KJ mol1)
B A1 Ga In T1
801 577 579 558 589

r
(i) O F (ii) F Cl
O

s
N


(i) t
(ii)



r


t
P P q

17
F>Cl>Br>I
s, p, d f
r
(i) ns2 np4 n=3
(ii) (n1) d2 ns2, n=4
(iii) (n2)f 7 (n1) d1 ns2, n=6

(kJ mol1
(egH) (kJ mol1 r
H1 H2 egH
I 520 7300 60
II 419 3051 48
III 1681 3374 328
IV 1008 1846 295
V 2372 5251 +48
r rr
93

VI 738 1451 40

(binary halide)

MX2 (X =

MX X =

p p

d d

(n)
(Z)

F, Ne Na+

(Z)
(n)
PP
94

n n

B, Al, Mg, K

B, C, N, F Si


F, Cl, O N

P P



P
CHEMICAL BONDING AND MOLECULAR STRUCTURE

qr r
st r s
s


















s, p
d








96

s s s
s s s s s

s
ss s s s s s s s s
s s s s s s s
s s ss s s s s s s s
s s s (Valence) ss s s
s
s s s t t r t tt
s P s s s t
s s s s s ss
s s s P s s s s s
s s ss s s s s s s s s
s s ss s s s ss s s s
s s s ss s s
s s s s ss s s ss s
s s s s s
s s s
P
s s s
s s s s s s s ss
s s s s s ns np s s s
2 6

s s s s s s s
s s s s s s s s
s (Na )
+

s (Cl ) s s s

s
Cl2, H2, F2, s s s s s
s s
P ss s
s s NaCl s
s s

s s s s s s +
Na Na + e
s s s s s s s 1
[Ne] 3s [Ne]
s qrt (Valence Electron) s Cl + e

Cl

s s (Inner Shell Electron)

[Ne] 3s 3p [Ar]
2 5 2 6
[Ne] 3s 3p
s s s s s + +
Na + Cl NaCl Na Cl
ss s
CaF2
s s s s s s s s 2+
Ca Ca + 2e
ss s s 2
[Ar]4s [Ar]
(Lewis Symbol) s
F +e F
s s s
[He] 2s 2p [Ne]
2 5 2 6
[He] 2s 2p
CaF2 Ca (F )2
2+ 2+
Ca + 2F

97

(Electrovalent
Bond)

(Electrovalency)

Cl Cl

s s

t sq

(Postulates)

P (Octet Rule)

q rst

(Sharing)

(Covalent Bond)

s

q (Single Covalent Bond)

(Cl2) s s

2 5
[Ne]3s 3p (Multiple Bonds)

Cl2

s s

q q t (Double
Bond) s

98

(Ethene)


CH4









C2H4 q
t t
t t N2 t q






(Skeletal Structure),



N2




C2H2
q
PP P P
q q (Ter-
P
minal Position) NF3
t

r
t
qs
(Formation) s






99

2 3 2 4
N(2s 2p ), O (2s 2p )
5 + (2 6) = 17
* P H P P
P

qrsts
17 +1 = 18

r NO2
CO

t
ONO
r
r

2 2 2 4
2s 2p 2s 2p

= 4 + 6 = 10
r CO CO
r C O

N O

C O
100

(Isolated)





t
qr q
q sr q
q q P
P P
r sr
q
P
t





(O3) O3
t t LiCl, BeH2
BCl3



Li, Be B
t

O
AlCl3 BF3


(Odd-Electron)
O (Odd)
t
NO


NO2
O




O3
t (Expanded)

3s 3p 3d

101

(Expanded Octet)

+
M(g) M (g) + e ; r

PF5, SF6, H2SO4 r X(g) + e X (g) ; r

+
M (g) + X (g) MX(s)

eg H r

(Electron Affinity)

r S

r r

P P P r

(Coulombic Interaction)

(Pack-
r r

ing) r
r

XeF2, KrF2, XeOF2

NaCl

r r

qs t

r (Lattice) r r

r r
102

Na Na 495.8
+

kJ mol Cl(g) Cl (g)
1

348.7 kJ mol
1

147.1 kJ (Value)
(788 J)



P





tqr s tqr t
AB
R = rA + rB R rA rB
P A B
NaCl
788 kJ mol
1

NaCl Na (g) Cl (g)
+

788 kJ









q


(Elec-
tron Diffraction)
rvdw rc



103

stt tt t ttt ts tt

t t t ss t t t t

t (pm)
OH 96
CH 107

NO 136
CO 143

CN 143

CC 154

P
C=O 121

N=O 122
C=C 133
C=N 138

CN 116
HOH CC 120

stt stt t t t t tt

t t t t

(pm)
H2 (H H) 74
F2 (F F) 144
Cl2 (Cl Cl) 199
Br2 (Br Br) 228
I2 (I I) 267

N2 (N N) 109

1 O2 (O = O) 121
kJ mol
HF (H F) 92
HH
HCl (H Cl) 127
1
435.8 kJ mol HBr (H Br) 141
1 HI (H I) 160
H2(g) H(g) + H(g); aH = 435.8 kJ mol
O2 stt s s t tt * rcov/(pm)
N2

O2 (O = O) (g) O(g) + O(g);

1

a H = 498 kJ mol
N2 (N N) (g) N(g) + N(g);
1

a H = 946.0 kJ mol

HCl

1
HCl (g) H(g) + Cl (g); aH = 431.0 kJ mol

H2O OH
*

r
104

H2O(g) H(g) + OH(g); aH1 = 502 kJ mol
1
I II

OH(g) H(g) + O(g); aH2 = 427 kJ mol
1

H
O H

O H
C2H5OH



P

O H

1 O [ I II
= 464.5 kJ mol
(Canonical) III
(Resonance Hybrid) ]

O O
O = O O O
(Bond Order) H2 st 148 pm 121 pm
q r O2 O3 O O
q N2 128 pm t O3
q st r r
CO r t I II
q r O3
N2 aH 946 O3
kJ mol r
1
(Resonance Concept)


F2

(Canonical)
N2, CO NO+


(Resonance Hybrid)

t O3 I

II
III
(Parameters)

P

105

stt s t t st

CO3
2

O3 III

I II

(I, II, III)

2
CO3 P P I, II P III r

r P

CO2

CO2

115 pm

(C = O)

(C O) 121 pm

110 pm
CO2

(115 pm), (C = O) (C O)

CO2

H2, O2, Cl2, N2 F2

CO2


(I, II III)
HF

CO2 P P P I, II, rPP III HF

r r PP P PP r q
106

(Dipole 30
6.17 10 Cm [ID = 3.33564
Moment) 10 Cm] OH
30








X-
q q


= 1.85 D

= 1.85 3.33564 10
30
C m
30
() = (Q) = 6.17 10 Cm

(r)
BeF2

(Debye)
(D)
30 (Cancel)
1D = 3.33564 10 Cm
C m ( + )
P s P


BF3


B F 120






HF


( + )= 0


rt t


BF3


NH3 NF3




(Vector sum) NH3

(4.9 1030 Cm) NF3
O H 104.5 Cm)
30
(0.80 10

107

NH3 (Fajans)

NF

NF

NF3

2 6
ns np

n o
(n 1) d ns

P P
P

P qrsP P t

(AB)
HF 1.78

HCl 1.07

HBr 0.79

HI 0.38

H2 0

(AB2)
H2O 1.85

H2S 0.95

CO2 0

(AB3)
NH3 1.47

NF3 0.23

BF3 0

(AB4)
CH4 0

CHCl3 1.04

CCl4 0
108

r P
P

r r P
t (Localised) t
P t
t r P
t P r
r (Sidgwick and Powell) P P P P
t r P P
P
(Nyholm and Gillespie) t
r
q s
t
t r P t t (i)
s s s
t r (ii)
P s s
r (Electron Cloud) P A
r P AB
r P
t
t P

(Distortion)
t t
t AB2, AB3, AB4,
r P (Spherical)
AB5, AB6

A r P B
r P

r P

P t
BF3 (AB3), CH4 (AB4)
PCl5 (AB5) t
t (Ball-stick) r
r
q
s
P P > P P >
(lp) (lp) (lp) (lp)
> P P

(bp) (bp)

109
110

()


111

AB2E 4 1

V-

120 119.5

AB3E

109-5 107

AB2E2

109.5 104.5
t
112

P PP P P P P P P PP P
P P P qrsPP PP
AB4E 4 1
90



90




(Folded)

AB3E2 3 2 T





ClF3
T-

p





(Bond Dissociation Energies)
t 1
H2 (435.8 kJ mol , 74 pm) F2(150.6 kJ
mol , 144 pm)
1

113

(Quantum
Mechanical)

(Molecular Orbital Theory)

(Heitler and London) P

(Pauling)

(Variation)

(Superposition)

H2
(H2)

A B

NA NB

eA eB
r

(i)

NA eA, NB eB

(ii)

74 pm

NA eB, NB eA

(i)
e A eB

(ii) q st q N A NB
114

H2 t s CH4, NH3
435.8 kJ H2O r t s t
r s
H2(g) + 435.8 kJ mol H(g) + H(g)
1
s s

t r s t s t
s
t s (amplitude)
r s r s s
s r
s s
t t t
t t s r
H2 H
s s
H2 p s s
P r



q r s t
s s r
s s ss
s
t t
s r s t t t t
t s
r s t t t
s s (Spin)
ss

s t s
s t r
t r s 1s

s
CH4, NH3 H2O t s
t t s
r CH4
s HCH t
10928' NH3 s p
s P

115

(Head on) (axial)

CH4, NH3 H2O

ss q

(Half Filled) s-

(CH4)

(Ground State)

2 2
t [He] 2s 2p
s-p q
1 1 1 1
[He] 2s 2px 2py 2pz
s-

p-

t t

t
t 1s
p-p q

CH p-

2p

90

HCH 90
(ii) qrs

CH 90

2s H 1s

CH

CH4

HCH

109.5

CH4

NH3 H2O HNH HOH

90 NH3
H2O 107
P PP P PPP P

104.5

P P PP P

PP

(i) () (ii) ()

(i) () qrs

116

CH4, NH3, H2O
sp

z-
s

sp
BeCl2 Be 1s
2

2s q 2s 2p
2

Be r (Pro-
mote) 2s 2p
sp 180
2s 2p sp 2p
sp3 Be Cl

(II) sp s
2

p sp2
BCl3
1s
2
P
2s 2p q 2s
2 1

2p
2s



(i)
(ii)

(iii) q
(iv) rs
r
rs
t s p sp
s, p d
BeCl2
(I) sp s p
sp 2p sp2
z- sp
s pz sp 2p
50% s- 50% p- B Cl BCl3

sp Cl-B-Cl 120

117

3
NH3 H2O sp
NH3

2 1 1 1
r
2s 2p 2p 2p x y z

3 3
sp sp

3

sp

3


sp

q
1s

NH s t

s s

s s

r NH3 s 109.5

sp
2
BCl3
107

q P
3
(III) sp

3
CH4 2s 2p sp

3 3
s p sp sp

3
sp 25% s- 75%
3 3
p- sp sp

3
P sp

109.5

NH3

3
sp

s 109.5

104.5 PP V-

s, px, py pz

3
sp CH4 H2O
118
3 2
sp , sp r sp (Sidewise)

C2H6 sp
3 P
sp3 sp3
CC sp2sp2
sp sp sp
3 3 3

pm p-
sp3 1s
sp3s CH (sp2-s)
C C 154 pm CH pm HCH HCC
109 pm 117.6 121
C2H4 sp
2

sp2

C C
C2H2 sp
sp2
sp s
2 sp 2py
2px 2py 2px

qst -

119

dsp2 d+s+p(2) [Ni(CN)4]2,

[Pt(Cl)4]2

sp3d s+p(3)+d PF5, PCl5

sp3d2 s+p(3)+d(2) BrF5

sp3d2 s+p(3)+d(2) SF6, [CrF6]3

d2sp3 d(2)+s+p(3) [Co(NH3)6]3+

s t t ss

sp

sp

C C

1s

qs t s
t

3

sp d

s p d

3
sp d

d-

r s d p

3s 3p d

4s, 4p 3p

4s 3p, 3d
4s

s, p d

3
(i) PCl5 sp d

(Z = 15)

2
3s
3d z PCl5 q q tq t
120

st
PCl5

sp d
3

P
P Cl

P Cl
(i)
120

(Equatorial) P Cl


(ii)
90 (Axial)
P

(iii)



PCl5



(ii) SF6 sp d SF6
3 2

3s2 3p4 (iv) P
s
p d
sp d
3 2


S F
SF6 (v)
P P

(vi)




(vii)




P
P ()
P (Amplitude)
P
P
SF6 qr

121

A qq
B t q qr r qq () qq

qq (*) q qqr q q q

(Approximation)

(Con-
(Linear Combination of Atomic
structive) (Destructive) (In-
Orbitals, LCAO) terference)

H2

A B

A B

1s

A B

(Nodal Plane)

= A + B



* = A B




PP P P

PP


P P

P P PP PP P P P

P P P P

qr stqq q A qq B st stqq qqr 1s 1s 2s

122

P 1s PP 2pz PP 2px PP
P PP P qP st
2s 1s
z-

r

123

2pZ 2pZ

2px 2py P q

O2, F2

1s < *1s < 2s < *2s <2pz<( 2px = 2py )
P
< *2px= *2py)< *2pz

Li2, Be2, B2,
C2, N2 q

q q t

q B2, C2, N2

1s < *1s < 2s < *2s < ( 2px = 2py) < 2pz
q
r 1s < *2px= *2py) < *2pz
s t

t
1s
1s* 2pz 2px 2py

[ ]

z-

2pz

t P P

2pz *2pz
t P

[ ] q

2px 2py
P
t

q
P s
Nb

s Na

[ ]
(i) Nb > Na
q P (ii) N > N
a b

q (i) P s

(ii)

s 1s
(Bond Order)
t

1s 1s

2s 2p s

P
2s, 2pz, 2px,

2py 2s, 2pz, 2px, 2py P

124

Nb > Na (He2)
1s
2

(Nb < Na) (Nb = Na) He2
1s 1s
t He2
t 2
He2 : (1s) (1s)
2

t
He2

He2

t Be2 [(1s)2 ( 1s)2
(2s) ( 2s) ]
2 2

tt 3. (Li2)
t
1s 2s
2 1

Li2


(Diamagnetic)
KK (2s)2
P
t t KK, K


(Paramagnetic)
P Li2 P





q r
Li2
s (H2) qt
P Li2
t qt 1s
t
q t
4. (C2) :
t 1s qt
(C2) 12

2
H2: (1s)

qt
t

C2

C2 P
qt q t
C2 C2
t
qt t t 438 kJ mol1 .
74 pm
qt
N2 t

125

5. (O2) :
r

2 2 4
1s 2s 2p




r t

8 16

O2 r
O2

*2px *2py
s s s s

r

P x P P P

O2

10 6
B2 Ne2

q 4.21

B2 Ne2
126

'X'
'X'

X








t


HF





(i)

(ii)
P P P (i)

HF

(ii)
t
qr (F,O,N) o-



s qr
qr q
(F,O N)


'X'





4.22 o-

127

P P

P r

qs

Pr

Pr

P P P P r

t P r

lp-lp > lp-bp > bp-bp

VB

P H2 P 1s

2 3
Be, B, C, N O sp, sp , sp BeCl2, BCl3,
CH4, NH3 H2O P

C2H2 C2H4 P

128

t (F, N, O)

P

Mg, Na, B, O, N, Br.

S S2, Al Al3+, H H

H2S, SiCl4, BeF2, , HCOOH



BeCl2, BCl3, SiCl4, AsF5, H2S, PH3
t NH3 H2O


P
PP s qr
P P H3PO3
H3PO3


129

SO3, NO2 r

K r S Ca r O Al r N
CO2 r H2 O r H2O r r r

t CO2 r r t

q r

s rr r t r q

t r
r t

r r qr

LiF, K2O, N2, SO2, r ClF3

CH3COOH r

r r CH4 r r t

t r t CH4

r r

BeH r BeH2 t

NH3 r NF3

2
r sp, sp r sp3 r

r Al r r r

r B r N r

s C2H4 r C2H2 r

r r r

C2H2 C2H4
x- r r r r

1s r 1s 1s r 2px 2py r 2py 1s r 2s

130

CH3CH3 CH3CH = CH2
CH3CH2OH CH3CHO
CH3COOH



H2

Be2



PCl5

P




STATES OF MATTER

P






rtrr q qrqrrs ts trq r r
rr
r
s
s
r
r r s
r
r

t
rr r
ts sqrqrr rrrrsq rts rrsrrrs s qrrqrrs rs rstr rr rsrtrsrrt rr ts
srqrqq
rrrrr rrr rs rt rs rrr rt rr r

s
tr ts s r r t s rr
r
r
t s rr
r r r r r t s r rr
r
r
t
r r s
r
q

r srs rrs rr rrrs rtts r rrrqrs rsr rr tr tsr
r s

H2O

r rrrr rrqs qrrt qrr r r rr r q r

r s rr rs s qrr rrsq r rrs qr rr rr tq rqr
r r r
r rs tq
qst r qr
r qtrs r rrrr r
r r
rqrrs rrrrqr r r r r s r qr
r r r t s r r
s s
r r
r r s r r

rqq r qqrr qr s rrs s t q r
rr rr rr r r r
r
s rt s tr
132

P






P
P qr st r
st












P P
A B q P q P
A
1/r 6 r
~500 pm
A


B


B


A B
()
(1.6 1019C)

133

HCl

1/r3 1/r 6
r







t

NH, OH HF

N, O F

Cl

kJ
mol1

P P
HCl P P

HCl q
rq
ss P

1/r6

r

(Cloud)

(Interaction)

134

q r
s t t

t














P P

XII


t



135

P
k1 k1

p
qr st
V

st r s r t

q pV = k1 (5.3)

T n (5.1) T p1 V1

V2 P2

(5.2)

p1V1 = p2V2 = (5.4)

(5.5)

k1

(Graph) rt

V p 5.1, 300 K CO2

136

300 K 0.09 CO2

/ / (1/V )/ pV/
104 Pa 103 m3 m 3 102 Pa m3

2.0 112.0 8.90 22.40

2.5 89.2 11.2 22.30
3.5 64.2 15.6 22.47
4.0 56.3 17.7 22.50
6.0 37.4 26.7 22.44
8.0 28.1 35.6 22.48
10.0 22.4 44.6 22.40

p r 1/V r
p2 = 0.2 bar r
r r
r r

r r
r bar r
r PP L r r
r r r r
r r
qst s
r
r r r r r r r
d, r V r m
r r
r r r r r r

r r r
r r r r 0 C r r

r r 0 r t C

r r r r r V0 r Vt r
r r




r r
r bar
r r r P (5.6)

bar L r r r r
r r r r r
r r tC Tt = 273.15
+ t r 0C T0 = 273.15 r
p1 V1 = p2 V2 r
p1 = 1 bar r V1 = 2.27 L (Absolute Temperature) r

137

00C; s k2

K V

P P

Tt = 273.15 + t T0 = 273.15
273.15 C

t
t C



(5.7) t

273.15 C
P


C
(5.8)

s s



(Ab-
q solute Zero)
s = k2 (5.9)
r

V = k2 T (5.10)

C P 2L

V1 = 2 L T2 = 26.1 + 273
T1 = (23.4 + 273) K = 299.1 K
= 296.4 K

(C)
138

P



t
P V n n
V = K4n (5.11)
6.0231023

q
r





(STP)* 273.15 K 1 bar
Pascal STP
22.7 L mol1

K bar (STP)





s K






(5.12)

m =



t (5.13)

* STP STP 0 Bar STP

Litre mol 1

(SATP)



STP
K

Bar Pascal STP

Litre mol1


139

n, R, T p


(5.14)

d
STP

K bar

Litre mol 1

= 8.314 Pa m3 K1 mol1 1Nm = 1J
= 8.314 102 bar L K1 mol1
PP P = 8.314 J K1 mol1
STP 0C

R = 8.20578 102 L atm K1 mol1

qrst rss t


p n VT


p T Vn


(5.15) T1 V1 p1 T2, V2

p2

(5.16)



R

(5.19)
pV = n RT (5.17)

(5.18)


R

p, V T 25C mm (Hg) mL

10C mL
140

p = p1+p2+p3+...... T, V (5.23)
p1 = 760 mm (Hg), V1 = 600 ml P p r P p1, p2,
T1 = 25 + 273 = 298 K p3 r P
V2 = 640 mL, T2 = 10 + 273 = 283 K P
P P P
P r r r
P
r P P


P
p = p (5.24)



p2 = 676.6 mm (Hg)

P P



T
n P P V r

p1, p2, p3 P q P
(5.20)
(5.25)



P d P (5.21)

(5.26)

P
(5.27)
q
P n1, n2, n3 q P
rs t P
p = p1 + p2 + p3

(5.22)



= (n1 + n2 + n3) (5.28)

p1 p P P



P r r

r
P r P n = n1 + n2 + n3
P P x1 P P P

141

p1 = x1 p

p2 = x2 p p3 = x3 p

pi = xi p (5.29)

t pi xi , i r

bar

P t

= 2.21 mol

= 8.375 mol

= 0.21

qs
s

= 1 0.21 = 0.79

= 0.21 25 (bar) = 5.25 (bar)

= 0.79 25 (bar) = 19.75 (bar)

142

pV p
pV
pV p
r 5.8, 273
K






r









qs t pV p qs
q



pV p




pV

r
pV




P


pV = nRT


143

t


q

(5.30)

t

q t

t


P

(i)

(ii) t
t V

(V nb)

t t nb

t
b

(5.31)

t
n

P t
a b

t a
P t

P
t

t t
144

Z
p, V nRT


(5.32)

Z = 1
pV = nRT Z p

Z

Z
Z 1


Z > 1 (5.33)

Z < 1 t
P



P t

q

r (5.34)



s s P
r
Z




Z
Z




145

30.98C 73

E 73

30.98C

(Tc)

(Vc) P (pc)

qrs r s qr s

21.5C B t

B t Z

t t

C C t

V2

V3 p2 p3

30.98C

A F t

31.1C

A D

D H t t

146

qs ts

























P


















K rK
K
bar


bar



100C (373K)

99.6C (372.6K)

147

P (Surface Tension)
t

qrr s qr r

rrs














t


Jm2

kgs2 SI Nm1

148

t t
t
t
(Fire-polishing)


t
t qrs
t t
t
P
t F A A P
t




t

tt t

t
t
t
t
P
SI
t t (Nsm2), Pas CGS
t
t t t
t 1 poise = 1 g cm1s1 = 101kg m1s1
t tt
t
t t
t t
t

t t t

dz du t
t t
t t


149

p ,V T p ,V T
1 1 1 2 2 2

pV =
nRT R

bar dm dm

bar mL

mL

C bar bar

bar

bar

bar C

150

C dm

C r bar r bar L
r r
C bar g dm STP

C bar mL g

C

C
bar dm mol r
(R = 0.83 bar dm mol
g r r
r

C dm r r

C m P
bar kg r r
= gm m R = bar dm mol
C bar CO2 r
R = 0.083 bar L mol1
2.9 g 95C 0.184 g r 17C

bar r r % r r
r
pV 2 T 2/n SI
C
C C




THERMODYNAMICS

t
P
P

rqr srrq q r rsr qq r qsr r s r rqsr

s rr sr r q sr q

q r r r sr qr
qr

U, H

q rqr qr r r
qrsqrsr r qr

U H

U H

H r sr rqssr qr rsr sr sqr rr r r qrsq

q qr q r qr q qr
r r sr s rr s q qr q

q qr qq sr q rsr r

qqr sr s sqrs srs qsqr r qs r r r r

r q r r qr
q s sr s
q r

( G)


G G
r r q s
qr r r q q qs
152

(Boundary)

t



t
t



P
(Open System)
t

P Exchange
P t
+ = P
(Closed system)
t P

P
(Isolated system)

t
t
A B
t *

qrs

(Cartesian coordi-
nates) (set)

qr
*
 153

t P

(p) (V) (T)

(Composition) (Specify)


P (Adiabatic)

P
P PP P

P

PPP

PPP

(p), (V), (T),

(n)
p, V, T

A TA UA

P P

q kJ
B
TB TB > TA


T = TBTA B

UB
r
U= UBUA
s r
P r
r
(Immersion Rod) s (kJ)
r U

TBTA

154

U,

wad U
U = U2 U1 = wad

wad
wad

q
V, p T
q
25C 35C 35C P
25C = +10C 35C
(Degree)
(35C)
T
U = q + w (6.1)

q w q + w =
U


w = 0 q = 0, U = 0
U = q + w,
q
P



q
TA r s
TB
q TBTA (Absolute) t
t
U = q U

 155

(i)

(w)

(ii)

(iii) w q

(i) U = wad'

(ii) U = - q,

(iii) U = q - w
= pex . A

qr t


Pex

P
w = x = pex.A.l
= pex . (V ) = pex V = pex (Vf Vi ) (6.2)



(Convention)


(Vf Vi )



w
Vi

p pex p



pex

Vf

= l A = V = (Vf Vi ) dV

s

156

P P pex = pin dp
( 6.3) P Pq pex = (pin + dp) r
st P Pq


(Reversed)





P r r Pq P
P r q
Pq
P
t
Pq



dp dV Pq

(6.4)

q pin q
Pq
q n r (pV = RT)



r





= 2.303 nRT log (6.5)

q (pex = 0)
pV Vi Vf P Pq q P
P P t P
r
P
Pq
pex (pin + dp) P w = pexV

 157

U = q - pexV qrst Enthalpy (H)

(V = 0)

U = qV , q V V (Subscript V )
P P PP

U = qV

T= w=0 pex= 0


q = 0 U=0

(U = q + w),

U = qp-pV

qp

-p V
q = w = pex (Vf Vi )

q = w = nRT ln = 2.303 nRT log

U2U1 = qp p (V2 V1)
q=0

U = w
ad
qp = (U2 + pV2) (U1 + pV1) (6.6)
PP

atm

H = U + pV (6.7)

q = w = pex (10 2) = 0(8) = 0 qp = H2 H1 = H

q qp

H H.U, p V
PP H

atm

q = w = pex (8) = 1 8 = 8 L
H = U + pV p
atm

PP

10 H = U + pV (6.8)
L

q = w = 2.303 10
H = qp

= 16.1 L atm
158

H s t q

U = H
H

(V = 0) U = qV,
H = U = qV

H U 1
= 37.904 kJ mol

P ii

P VA
VB P nA

nB P
P r
pVA = nART

pVB = nBRT
P
pVB pVA = nBRT nART = (nBnA)RT

p (VB VA) = (nB nA) RT
P r
p V = ngRT (6.9)
P
ng P


p V

H = U + ngRT (6.10) P r P P
H U U H Cm
P n

P Vm
P 100C 1 bar Cm
P V T
41kJ mol
1


i 1 bar P 100C

ii

i
V T
 159

Cp CV P

CV t

Cp

q t

qV =

t qp = s s

t V/2 t Cp t CV

t t H = U + (pV )
P
= U + (RT )

= U + RT
t
s s s (6.12)
r

H t U
r

s s s
q = x T
t r

(6.13)
'q = C T
C
U H

r


t
C r



(Calorimetry)
t
t t

t
C
t

Cm t


t
t

t t t

i
qV ii qp

t t t

t (Bomb calorimeter)

q t t

C m t T

(Sample)

q q s s (6.11)
160

r
V = 0

qV

g r
atm K

C r P + O2 (g) CO2 (g)
K K
kJ/
K atm
K rq

s
H
t q
P
CV
r

H = qp P
q = CV T
qp
rH t r
r P
qp r r
r rH r r
r qp
rH r
 161

1
g
U = -20.7 kJK

K bar
2 1
= 2.48 10 kJ mol

ng = 0
2 1 K bar
U = 2.48 10 kJ mol
K bar

P K

H P H Superscript
r

r
H

r
H =

rst q
(6.14)

fus

ai bi

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l)

fus


= [Hm (CO2 ,g) + 2Hm (H2O, l)] [Hm (CH4 , g) +

2Hm (O2, g)] Tb

Hm



vap

Tf Tb

vap
162

Substance Tf/K fusH /(kJ mol1) Tb/K vapH0/(kJ mol1)
N2 63.15 0.72 77.35 5.59
NH3 195.40 5.65 239.73 23.35
HCl 159.0 1.992 188.0 16.15
CO 68.0 6.836 82.0 6.04
CH3COCH3 177.8 5.72 329.4 29.1
CCl4 250.16 2.5 349.69 30.0
H 2O 273.15 6.01 373.15 40.79
NaCl 108.10 28.8 1665.0 170.0
C6H6 278.65 9.83 353.25 30.8

(dry ice) sub = t
25.2kJ mol -1



sub = 73.0 kJ mol -1
P P P P 18g H2O (1)

P PP

P P q
rs t


t t

t

t rr



t
t rs
f
P P P P P P P
Pool g P P P P P PP P
K PP P P P
PPP P P
100C t t f q
f
373 K =40.66 kJ mol
-1
Vap
 163

C , s



P

s qr rt


HBr (g)

f


f r
164

r r CaCO3(s)






rH


HBr(g)
q



P
q st K
f


f





q
r

r kJ mol-1








(6.15) = 285.83 kJ mol ; 1

s = 824.2 kJ mol
a b 1
;

f H (Fe, s) = 0
0

a b
f H 0 (H2, g) = 0,


r = 3(285.83 kJ mol 1
)
1( 824.2 kJ mol1)
= (857.5 + 824.2) kJ mol1
= 33.3 kJ mol1

= 178.3kJ mol 1 Stoichiometric
 165

coefficients
f
kJ mol-1
t

CO (g) t

CO2
s s

P t

(i)
r

= ( 428.7 + 412.1) kJ mol1

= 16.6 kJ mol = 1

(ii)
r


t



q
CO(g) (ii)

(iii)


(i) (iii)

s



r



t

= 110.5 kJ mol1

rH = rH1 + rH2 + rH3 ... (6.16)



166

rH 298 K 1 atm
A B
CO2(g) H2O (1)
rH1 rH3
3267.0 kJ
rH2
C D CO2(g)
H2O (1)
393.5 kJ mol1 285.83 kJ
mol
1





c
P

CO2(g)
(C4H10)
2658

kJ



H2O (1)

q r st st q st r s



2802.0 kJ/mol

iii iv 3








 167

(i)

(ii)
ii

v vi
H2(g) 2H(g) ;
HH
H = 435.0 kJ mol1
HH
qr
st r t (Bond Dissociation

Enthalpy)

Cl2(g) 2Cl(g) ;
ClCl
H = 242 kJ mol1
HH H O2(g) 2O(g) ;
O=O
H = 428 kJ mol1

a
H

(Polyatomic Molecules) :

CH4

CH4(g) C(g) + 4H(g); aH = 1665 kJ mol1
C-H

C H C-H

Na(s) Na(g) ;
a

H = 108.4 kJ mol 1
C-H

H
bond

168

P P
P P s P P P t
P P s P P
CH4 C-H
s P
P

= 416 kJ mol1

(6.17)**
C-H P
P 416 KJ/mol P t

P s
t CH3CH2Cl, CH3NO2 C-H
P * P s s
P P t
P P P t P P t
P P P q r P
s P P P t s P
P s P

K (kJ mol1

H C N O F Si P S Cl Br I
435.8 414 389 464 569 293 318 339 431 368 297 H
347 293 351 439 289 264 259 330 276 238 C
159 201 272 - 209 - 201 243 - N
138 184 368 351 - 205 - 201 O
155 540 490 327 255 197 - F
176 213 226 360 289 213 Si
213 230 331 272 213 P
213 251 213 - S
243 218 209 Cl
192 180 Br
151 I

K kJ mol 1

N=N 418 C=C 611 O = O 498

N N 946 C C 837
C=N 615 C=O 741
C N 891 C O 1070

*
** (fH bond)

 169

So1
H P

(Born-Haber cycle)

t AB (s)

AB(s) s

P
NaCl

Na+Cl

q
s

q

t
q P

r




P

170

NaCl(s)






sol H
P
P
qr s qt q
qt qt s s q qt s NaCl(s)
sts qr s t s
qts s s

q T qt q qt st s
qts s s



qt t s qr s
t

q
st

q = E0


q

(Driving Force)

s
r r



r


tt




s
2 RT
+ 783 kJ mol1.

(Agency)
 171

(Agency)

r q s t q

qs

N2(g) + H2(g) NH3(g) ;


r
H = 46.1 kJ mol1

H2(g) + Cl2(g) HCl (g) ;
r

r
H = 92.32 kJ mol1 s

H2(g) + O2(g) H2O(l) ;



r
H = 285.8 kJ mol 1
P

q
t r r
s
()
s r

s r r s
t

r t (Driving force)
t q (Isolated)
t

s q s
N2(g) + O2(g) NO2(g);
q

r
H = +33.2 kJ mol1
C (q
, s) + 2 S(l) CS2 (l); q A Bs

r
H +128.5 kJ mol 1 t q r r

q t

r r q s t q q

6.10 ()
172

(Quantify)



t
U
H
S


P (q)

P S q
r
q
r A s
B
s
r q
A B

S q T
r


(6.18)

r

S (Stotal) s
r

(6.19)

s
r S = 0


 173

1 1
q ss r
549.4 JK mol 298 K
Ssys =

tt

(i)



(ii) 0 K 115 K T

(i)

(ii) 0 K

115 K

(iii) NaHCO3

tt

(iv)

174

G


G = H - TS (6.20)

G

ss
(6.22)

Hsys

G

(subscript)

(6.21)
(i) (< 0)
=

P (ii) (> 0)

H
S
P TS H
G H
TS [ TS = (K) (J/K) = J] T

T
Stotal = Ssys + Ssurr P
P
P (Summarise)
P


P


q
r r

tt (i)
tt
(ii)

TStotal = T Ssys Hsys


 175

r
G
r
S

K


r
S





(i) H S G

(ii) K

G

r
G=0
qs t

298 K

r
G,


r G

0 = rG + RT ln K Kp

29

r
G = RT ln K 2.4710

r
G = 2.303 RT log K (6.23)

r G = 2.303 RT log Kp R


r

r

r
(6.24) = 8.314 JK
1
mol
1

r
H

K
G =
r
2.303 (8.314 J K1 mol1)


(298 K) (log 2.47 1029)
P

G

= 163000 J mol1
r

K = 163 kJ mol1

r
H
r
S
r
G s *

+ + +

+ +

+ +

*
176

298 K






r

-1
13.6 kJ mol







=

P
= 2.38
K = antilog 2.38 = 2.4 10
2 = 1.33 atm.

G = RT ln K
qqst sst q 50 % r p

q rG = (8.314 JK mol )
1 1
(333 K)
1
(2.303) (0.1239) = 763.8 kJ mol

(q ) (w)
U = q + w U
U q w
q w

(C) q = CT
W = pexV
pex = p W rev = pdV pV = nRT

w = 0 U = qv

 177

tP tP

q s

S,

(i)

(ii)

(iii)

(iv)

(i) T = 0 (ii) p = 0
(iii) q = 0 (iv) w = 0
178

(i) (ii)
(iii) < 0 (iv)
U X kJ mol1 H

(i) = U 0 (ii) > U 0
(iii) < U 0 (iv) = 0

298 K 890.3 kJ
mol 393.5kJ mol 285.8 kJ mol1 CH4(g)
1 1

(i) 74.8 kJ mol1 (ii) 52.27 kJ mol1

(iii) +74.8 kJ mol1 (iv) +52.26 kJ mol1.
q

(i) (ii)
(iii) (iv)
701 J 394 J

NH2CN(s) U
742.7 KJ mol1 298 K 298 K


NH2CN(g) + O (g) N2(g) + CO2(g) + H2O(l)
2
60.0 g 35C 55 C
Al 24 J mol1 K1
P 10.0C P 10C
fusH = 6.03 kJ mol1 0C
Cp [H2O(l)] = 75.3 J mol1 K1
Cp [H2O(s)] = 36.8 J mol1 K1
PP CO2 393.5 kJ mol1 35.2 g CO2

P CO(g), CO2 (g), N2O(g) N2O4(g) -110,-393, 81
9.7 kJ mol1 N2O4(g) + 3CO(g) N2O(g) + 3CO2(g) r

P N2(g) + 3H2(g) 2NH3(g); NH3

P CH3OH(l)

CH3OH (l) + O (g) CO2(g) + 2H2O(l) ; rH s = 726 kJ mol1
2
C + O2(g) CO2(g) ; cH = 393 kJ mol1
t
H2(g) + O (g) H2O(l) ; f H = 286 kJ mol1.
2
 179

C Cl

vap
H (CCl4) = 30.5 kJ mol1.

f
H (CCl4) = 135.5 kJ mol1.

a
H (C) = 715.0 kJ mol1 ,
a
H0

a
H (Cl2) = 242 kJ mol1
U = 0, S

298 K

H SQ

s t
r

R = 8.314 JK mol 1 1

N2(g) + O2(g) NO(g);
r
H = 90 kJ mol1

NO(g) + O2(g) NO2(g):
r
H = 74 kJ mol1

H2O(l)

EQUILIBRIUM

P

P
O2

P
O2

CO CO

t qs
r s

r P
s

r r
Kp Kc


P P

s
(System)

r r P
r r r

H2O H 2O

P
pH
P
P
r

t
r (KW)

s
P

pKW

s
(Dynamic

r
Equilibrium)

 181

t
s

(i) st

273 K

(ii)

(iii) r

(i)

(Operational Conditions)
(ii)
st

(Optimize)

(Phase Transformation Processes) t

(Insulated) q st

t

273 K

t

182

t t 1.013
bar t
t t t r
r t r
t t r
H2O H2O r
t t
P
t
t r t t
r t r t t
t
t r t r
t r
r r
t t
1 mL t
t I2
I2
t t
t r

(i) t (ii) t (iii) NH4Cl NH4Cl
r
P P qs s
r t
s
r
t t t r
t r t
t r
r r t
t t r
(1.013 bar) 100C r t t
1.013 bar t 100C r (Saturated)
 183

(i) r

(1.013 bar) r

=
(i) r

(iii)

(Non-radioactive)

r
(iv)

qs

H2O (l) H2O (g)

t r H2O (s) H2O (l)

(aq)/ (g)

(g) (aq)

CO2

CO2

r
CO2 (g) CO2 (aq) [CO2 (aq)]/[CO2 (g)]

P P

CO2 t
t

(i) (Closed System)

(ii)

r
t

r
(iii) t

(iv)

r
184

qr s t

(v) P

r
t P



t
P
P

t q
H2
D2 (Deuterium) H2 D2
P
q q
H2 NH3 D2 ND3
H2,
N2, NH3 D2, N2, ND3
A+B C+D
(A B) t
P (C D)
P
t P P

(Mass Spectrometer) s

P (NH3, NH2D, NHD2

ND3) H2, HD D2
C D
tt


A + B C + D C + D A + B
H D (Scram-
bling)


t (Deuterium)
tP



s
H2(g) N2(g) NH3(g)
NH3(g) P N2(g)
H2(g)
 185

100 mL 30 cm

3 5 mm

qrs t t
186

H I

q
r
s





(H2, NH3 CaO)

N2(g) + 3H2(g) 2NH3(g)

2NH3(g) N2(g) + 3H2(g)

H2(g) + I2(g) 2HI(g)
A+BC+D
H2 I2 A B
C D
H2 I2 HI
(Cato Maximillian Guldberg)
t P HI (Peter Waage)
HI
H2 I2
t P
(7.1)

Kc
r s
r s (Law of Mass
Action)

(Sealed Vessel) 731
K H2 I2


H2(g) + I2(g) 2HI(g)
1 1 2
H2(g) + I2(g) 2HI(g) t
H2 I2
 187

P P P H2, I2, HI

HI

H2 = I2
(7.1)

= HI

[H2(g)]eq = [I2(g)]eq

(Power)

(Stoichiometric Coefficients)

'Kc'

P
q
H2(g) + I2(g) 2HI(g) Kc ,

H2(g) + I2(g) r 2HI(g)

(7.2)

'eq' s

Kc

(7.3)


188

'c' Kc P P

mol L1 P (7.7)

(7.8)

qrsr r rsrrr rr
qrsr rsrrr rr s rr

aA + bB cC + H2(g) + I2(g) HI(g) (7.9)
cD

Kc = [HI] / [H2]1/2[I2]1/2 = x1/2 = Kc1/2 (7.10)

(7.4) n

nH2(g) + nI2(g) 2nHI(g)
C D Kcn
A B [C],
[D]


4NH3 + 5O2 (g) 4NO(g) + 6H2O(g) rrs r rsrrr
rr
aA+bB c C + dD Kc
cC+dD Kc =(1/Kc )
aA+bB

(Species) na A + nb B ncC + ndD Kc = (Kcn )

Kc K'c







rr

t (Fac-
tor) 500 K N2 H2 NH3

[N2] = 1.5 10
2
M, [H2] = 3.0 10
2
M
H2(g) + I2(g) 2HI(g) (7.5) 2
[NH3] = 1.2 10 M.


(7.6)

2HI(g) H2(g) + I2(g) N2(g) + 3H2(g) 2NH3(g)

 189

pV = n RT

= 0.106 104 = 1.06 103

(p) bar

'n' 'V' (L)

800 K N2(g) + O2(g) 2NO(g)

(K)





3 3
N2=3.0 10 M, O2 = 4.2 10 M 'R' 0.0831 bar L mol1K1 s
3
NO = 2.8 10 M n/V mol/L

Kc
t
'c' s

p = cRT
q t

p q

p= RT s

P


H2(g) + I2(g) 2HI(g)





= 0.622

(7.12)


qr

s qt


N2(g) + 3H2(g) 2NH3(g) qr

CH3COOC2H5 (aq) + H2O (l) CH3COOH (aq)

+ C2H5OH (aq)

Fe 3+
(aq) + SCN(aq) Fe(SCN) 2+ (aq)

qr

s



s
(7.13)

( Kp )
qr t

q qt Kp = Kc,

r s
Kc s

qt N2(g) + 3H2(g)

s 2NH3(g)
190

500 K PCl5, PCl3 Cl2
1.41 M, 1.59 M 1.59 M
PCl5 PCl3 + Cl2 Kc




(7.14)


aA + bB
cC + dD


P

P
800 K Kc = 4.24
r s
r sq t q CO (g) + H2O (g) CO2 (g) + H2 (g)
t
800 K CO2 H2, CO H2O


CO H2O

(7.15)
0.1 M
n = [


] Kp
bar CO (g) + H2O (g) CO2 (g) + H2(g)
1 bar 1
pascal, Pa = 1 Nm2 1 bar = 105Pa 0.1M 0.1M 0 0

Kp
(0.1x)M (0.1x)M xM xM
CO2 H2 x mol L1

Kp
2 2
Kc = x /(0.1 x) = 4.24
2 2
x = 4.24(0.01 + x 0.2x)
2 2
x = 0.0424 + 4.24x 0.848x
2
3.24x 0.848x + 0.0424 = 0
a = 3.24, b = 0.848, c = 0.0424
ax2 + bx + c = 0,




x = 0.848
 191

bar 4 bar
x = (0.848 0.4118)/ 6.48 4 bar/ 1 bar = 4

x1 = (0.848 0.4118)/6.48 = 0.067 (C ) 1

O


x2 = (0.848 + 0.4118)/6.48 = 0.194

0.194
Kp
Kc

[CO2] = [H2-] = x = 0.067 M

[CO] = [H2O] = 0.1 0.067 = 0.033 M P

2NOCl(g) 2NO(g) + Cl2(g)

H2O(l) H2O(g)
1069 K Kc 3.75
6
10 Kp

Ca(OH)2 (s) + (aq) Ca 2+
(aq) + 2OH(aq)
P

n
P
Kp = Kc(RT)

n = (2+1) 2 = 1

6
Kp = 3.75 10 (0.0831 1069)
'X'

Kp = 0.033
[X(s)] [X(l)]

'X' [X(g)]
[X(aq)]

P


Kc
mol L1


Kp Pa,

CaCO3 (s) CaO (s) + CO2 (g) (7.16)

kPa, bar atm

qrs t qs




qrqs t

H2(g) + I2(g) 2HI, Kc Kp

[CaCO3(s)] [CaO(s)]
N O (g) 2NO2 (g), Kc mol/L
2 4

Kp bar
K'c = [CO2(g)]

(Dimensionless)
P CO2(g)
192

CaO(s) CaCO3(s) (0.48 x)bar 2x bar

1100 K CaCO3(s) CaO (s)

CO2 2.0 105 Pa
2
Kp = (2x) /(0.48 x) = 3
2
4x = 3(0.48 x)
2
P P
4x = 1.44 x
2
4x + 3x 1.44 = 0

a = 4, b = 3, c = 1.44




Ni (s) + 4 CO (g) Ni(CO)4 (g)

= [3 4(4)(1.44)]"/2 4


= (3 5.66)/ 8
x

x = 2.66/8 = 0.33


= 2 x = 2 x 0.33 = 0.66 bar

= 0.48 x = 0.48 0.33 = 0.15 bar

Ag2O (s) + 2HNO3 (aq) 2AgNO3 (aq) + H2O (l)






qrsts
CO2 (g) + C (s) 2CO (g),
1000 K Kp 3.0


bar = 0 bar

CO CO2

t

CO2 x
K
CO2 (g) + C (s) 2CO (g)

0.48 bar 0
 193

3 3
Kc 10 10 (Range)

700 K H2 I2 HI Kc = 57.0

Kc qs t t t

N2O4 NO2

3
25C Kc = 4.64 10

Kc Kp

N2O4 NO2
r

(Numerator)

(Denominator)

(Reaction Quotient) 'Q'

3
K c > 10
Qc
K Qp

500 K H2 O2 aA+bB cC+dD

47
Kc = 2.4 10 (7.19)
300 K H2(g) + Cl2(g) 2HCl(g); Qc = [C] [D] / [A] [B]
c d a b
(7.20)
31
K c = 4.0 10 Qc > Kc

300 K H2(g) + Br2(g) 2HBr(g);

18
K c = 5.4 10 Qc < Kc

3
Kc < 10

Kc P
Qc = Kc

H2 I2

500 K H2O H2 O2

48
Kc = 4.1 10 H2(g) + I2(g) 2HI(g)
298 K N2(g) + O2(g) 2NO(g); 700 K Kc = 57.0
31
K c = 4.8 10 [H2]t=0.10M, [I2]t = 0.20 M
194

[HI]t = 0.40 M. [A] = [B] = [C] = 3 10

4
M
t

t


Qc Qc > Kc

Qc = [HI]t2 / [H2]t [I2]t = (0.40)2/ (0.10)(0.20) = 8.0
qs tt
Qc (8.0), Kc (57.0)
H2(g), I2(g) HI(g)

H2(g) I2(g) HI(g)
r
r Qc = Kc 1 :
2 :
Qc, Kc
r


Qc < Kc
x
Qc > Kc
x
Qc = Kc 3 : x



4 :

5 :

13.8 N2O4 1 L

2A P B + C Kc
3
N2O4(g) P 2NO2(g)
2 10
9.15 bar
[A] = Kc, Kp
4
[B] = [C] = 3 10 M




pV = nRT

(V) = 1 L
 195

2
(N2O)4 = 92 g 1.8 = x / (3 x)
2
= 13.8 g/92 g x + 1.8x 5.4 = 0
2
= 0.15 x = [1.8 (1.8) 4(5.4)]/2

(R) = 0.083 bar L

1 1
K x = [1.8 3.24 + 21.6]/2

r = 400 K x = [1.8 4.98]/2

pV = nRT x = [1.8 + 4.98]/2 = 1.59

p 1 = 0.15 0.083 bar L [PCl5] = 3.0 x = 3 1.59 = 1.41 M

1 1
mol K 400 K [PCl3] = [Cl2] = x = 1.59 M

p = 4.98 bar
K,

N2O 4 2NO2
qs Q G

4.98 bar 0
Kc r
(4.98 x) bar 2x bar
r t

r p


r r t

9.15 = (4.98 x) + 2x r r

9.15 = 4.98 + x G r r r r

x = 9.15 4.98 = 4.17 bar tr r r

G r r r r

= 4.98 4.17 = 0.81bar t r r G

r r r

= 2x = 2 4.17 = 8.34 bar
t







G r r

2
= (8.34) /0.81 = 85.87

n
Kp = Kc(RT) r r
1
85.87 = Kc(0.083 400) t r

Kc = 2.586 = 2.6 G = G + RT lnQ (7.21)

t G
t

t G= 0 r Q = Kc r
380 K 3.00 PCl5 1L

tr r t

G = G + RT ln K = 0 (Kc K r

Kc = 1.80

G = RT lnK (7.22)
lnK = G / RT
PCl5 PCl3 + Cl2
r

3.0
0 0

t PCl Pr x mol tr

(7.23)
5
r r
r G

(3-x) x x
rr r t r

G < 0 r G /RT r
Kc =




K>1 t rrr
196

N2 H2

G > 0 G/RT
, K < 1 100


Kc





G 13.8 kJ mol 298 K
1

Kc

q
G = 13.8 kJ mol1 = 13.8 103 J mol1
G = RT lnKc
ln Kc = 13.8 10 J/mol
3

8.31 J mol1 K1 298 K)

ln Kc = 5.569
Kc = e
5.569 r
Kc = 3.81 10
3
s
tq
s

+ H2O +
300 K
300 K G
13
Kc, 2 10



G = RT lnKc t
G = 8.314 J mol1 K1
13
300K ln(2 10 )
G = 7.64 104 J mol1

P P PP
s

tq


 197

Qc = [HI]2/ [H2][I2]
H2 [H2]
Qc Kc

[H2]

[I2] [HI] Q c = Kc
r

H2(g) + I2(g) 2HI(g)

r H2

H2

H2 I2 HI

CaCO3 CaO

CO2

t Qc

r Kc

(7.25)

t (III) 1mL

[Fe(SCN)] 2+

P
[Fe ]/[SCN ]
3+

H2

qs (H2 C2 O4), Fe3+

198

[Fe(C2O4)3]3 [CO], [H2], [CH4] [H2O]

Fe3+
Fe3+
[Fe(SCN)]2+ Fe3+
[Fe (SCN)]2+
q r
s
HgCl2 q q r
Qc < Kc
Hg2+ SCN P P
[Hg (SCN)4]2
SCN [7.24]
SCN
SCN















(Q) (Kc)

P P (Kc)
(CO + 3H2) H
(CH4 + H2O)
t H

t H









Qc
t
 199

NO2 N2O4 (Dimerization)

[Co(H2O)6] 3+

HNO3 P NO2

5mL

(araldit)

(stopper)

250mL 1, 2 3

1

(Freezing

mixture) 2

3 (363K)

2

NH3

8 - 10

N2O4 NO2

NO2

NH3
P

NH3

NH3

P 500C 200

q st

SO2 SO3
200

(V2O5)

100%
5%


r s


P q q P q



t
t L




Acidus

(Book binder)
(Davy)


(Royal Institute Laboratories)
(First Fullerian Professor)
(17911867)




(Disseminated)


 201

HX

H+

t
t

H3O+

H (aq)+
H3O (aq) +

H+(aq) H3O+(aq)

MOH

+
P P Na Cl =1013cm

H3O+

H O Cl
+


3

H5O , H7O +
2
+
3
H9O4+

t
H3O2 , H5O3

t (<5%)
H7O
4

qq r

+
s
H9O4
202

(Thesis)


t

r

(1859-1927)
(Immuno Chemistry),
(Cosmology), (Origin In Life) (Cause Of Ice Age)

q q q r

OH s
OH H2O OH

NH3 t r


H2O
P OH NH3
s


H+

H+



HCl (aq), H2O
NH3 H2O H2O

 203

tt
qrs

HCl

s

H3O+ Cl HCl

HCl, Cl

H2O H3O+

H3O+, H2O

BF3 NH3

HCl

BF3 NH3

BF3 + :NH3 BF3:NH3

HF, H2SO4 HCO3 AlCl3, Co3+, Mg2+

H2O,

NH3, OH

F , HSO4

HCO3

NH2, NH3 HCOO

+
HO F H BCl3

+
NH3, NH4 HCOOH

H2O, HCO3, HSO4 NH3

BCl3

+
H2O H3O OH
2
HCO3 H2CO3 CO3
2
HSO4 H2SO4 SO 4

+
NH3 NH4 NH2

204

(HClO4) (HCl), HClO4, HCl,
(HBr) (HI), HBr, HI, HNO3,
(HNO3) (H2SO4) H2SO4
ClO4, Cl, Br, I, NO3 H2O

(LiOH), HA
(NaOH), (KOH), (HNO2),
(CsOH) (HF) (CH3COOH)
Ba (OH)2,
H3O OH NH
2
, O2 H H2O
OH
r s
(HIn) (In)

t
HA

q q q
H+







s HA
s
HA H3O+ B
s H2O
s

HA, H3O+ HA s
H3O+ A H2O(l) + H2O(l) H3O+(aq) + OH(aq)
H3O+
P P P

K = [H3O+] [OH ] / [H2O] (7.26)

[H2O]
 205

Kw = [H+] / mol L1

pH

+
Kw = [H ][OH ] (7.27)

298 K H+

pH = log aH+ = log {[H+] / mol L1}
1.0 10 M 7
H +
HCl (102 M) pH
OH

=2 NaOH

[OH ] = [H+] = [OH] = 104 [H3O+] = 1010 M

1.0 10 7 M pH = 10 298 K

298 K Kw


10 M 7


Kw = [H3O+][OH ] = (1 107)2 = 1 1014 M 2
pH = log (10 ) = 7 7

(7.28)
pH 7
Kw
pH 7

1000 g/L

18.0 g /mol
pH < 7

pH < 7
[H2O] = (1000 g /L)(1 mol/18.0 g) = 55.55 M.
pH = 7

298K

+
Kw = [H3O ] [OH ] = 10 14

10 7 / (55.55) = 1.8 109 or ~ 2 in 109

log Kw = log {[H3O+] [OH]}

= log [H3O+] log [OH]
= log 1014
H3O +
OH

pKw = pH + pOH = 14 (7.29)
Kw

[H3O+] > [OH ]

[H3O+] = [OH ] pH

[H3O ] < [OH ]

+

pKw
pH

(Logarithmic Scale)
pH pH

pH P
[H ] +

10

10 pH

[H ] +
100 pH 2
(<0.01M)

(H+) pH

r t

pH pH

pH t
206

pH
pH 8
1.0 10 M HCl pH
pH 1-
14 pH 0.5
2H2O (l) H3O (aq) + OH (aq)
+

14
Kw = [OH ][] = 10
+
x=[OH ]= H3O
+
H3O (i) t HCl

+
HCl (aq) + H2O (l) q H3O (aq)+Cl (aq)
(ii)
+
H3O
pH pH + 8
[H3O ] = 10 +x
8
Kw = (10 + x)(x) = 1014
pH 2 8 14
x + 10 x 10 = 0
pH 8
[OH ] = x = 9.5 10
P pH 0.001
r rr pOH = 7.02 pH = 6.98
pH P pH
s
7.5
r
HX
HX H+(aq)
3
3.8 10 M pH X(aq)


HX(aq) + H2O(l) q H3O+(aq) + X (aq)
3
pH = log[3.8 10 ]= {log[3.8] + (M)
3
log[10 ]} c 0 0
= {(0.58) + ( 3.0)} = { 2.42} = 2.42
pH 2.42 (M)
-c +c +c

pH
pH pH
NaOH ~15 5.0
0.1 M NaOH 13 ~4.2
10.5 ~3.0
10 ~2.2
7.8 ~1.2
7.4 lM HCl ~0
6.8 HCl ~1.0
6.4
 207

(M) pH t

c-c c c

t c= t HX
t r

r = HX
t

t r r t t
t

Ka = c 2
2
/ c(1- ) = c
2
/ (1- )
P Ka r

Ka HX P t t

Ka = [H+][X] / [HX] P t
(7.30)
c
Ka HX

Ka

Ka

r r

1M

P r

t
pH
pH
pKw
pH = log [H3O+]

pKa = log (Ka) (7.31)
r Ka r c HF r

0.22M
HF
r
+
r H3O , F r HF
pH
r pH t

K P

qs (Ka)
r

+ 4

(HF) 3.5 10 4 (1) HF + H2O H3O + F Ka = 3.2 10
+
(HNO2) 4.5 10 4 (2) H2O + H2O H3O + OH
14
(HCOOH) 1.8 10 4 Kw = 1.0 10
(C5H4NCOOH) 1.5 10 5
Ka >> Kw,

(CH3COOH) 1.74 10 5 +
5
HF + H2O H3O + F
(C6H5COOH) 6.5 10
(HCIO) 3.0 10 8
(M)

(HCN) 4.9 10 10 0.02 0 0 (0)

10
(C6H5OH) 1.3 10 (M)
208

0.02 +0.02 +0.02 = [HA]P/[HA] 100% (7.32)

(M)
0.02 0.02 0.02 0.02
0.08 M (HOCl)
pH
2
Ka = (0.02) / (0.02 0.02) = 0.02 / (1
2 2.5 10
5
HOCl
) = 3.2 10
4


2 2 2
+ 1.6 10 1.6 10 = 0 +
HOCl(aq) + H2O (l) H3O (aq) + ClO (aq)

(M)
= + 0.12 0.12 0.08 0 0
= 0.12 (M)
= 0.12 x +x +x
HF, F H3O+ (M)

+
0.08 x x x
[H3O ] = [F ] = c = 0.02 0.12 = +
3 Ka = {[H3O ][ClO ] / [HOCl]}
2.4 10 M 2
= x / (0.08 x)
[HF] = c(1 ) = 0.02 (1 0.12) =
2 5
-3 x / 0.08 = 2.5 10
17.6 10 M
2 6 3
+
pH = log[H ] = log(2.4 10 ) = 2.62
3
x = 2.0 10 , x = 1.41 10
+ 3
[H ] = 1.41 10 M.

0.1M pH 4.50
H+,A HA
= {[HOCl]P / [HOCl]}
Ka pKa 3
100 = 1.41 10 / 0.08 = 1.76 %.
3
pH = log(1.41 10 ) = 2.85.

+ qr st
pH = log [H ]
+ pH 4.50 5 MOH
[H ] = 10 = 10 = 3.16 10
+ 5

[H ] = [A ] = 3.16 10 MOH(aq) M+(aq) + OH(aq)
+ -
Ka = [H ][A ] / [HA] (MOH)
-5 M+ OH
[HA] = 0.1 (3.16 10 ) 0.1

5 2 8
Ka = (3.16 10 ) / 0.1 = 1.0 10 Kb
pKa = log(10 ) = 8
8


Kb = [M+][OH] / [MOH] (7.33)

c =

=
 209

t + 14 10
[OH ] = Kw / [H ] = 1 10 / 1.67 10
t
5
Kb
= 5.98 10

t

r

298 K

0.004 M t

Kb +
Kb= [NH2NH3 ][OH ] / [NH2NH2]
P (CH3)2NH 5.4 10 4 5 2 7
= (5.98 10 ) / 0.004 = 8.96 10
P (C2H5)3N 6.45 10 5 7
pKb= logKb = log(8.96 10 ) = 6.04.
NH3 or NH4OH 1.77 10 5
1.10 10 6

C5H5N 1.77 10 9 0.2M NH4Cl 0.1 M NH3

P C6H5NH2 4.27 10 10
pH t NH3
CO (NH2)2 1.3 10 14
pKb = 4.75

t +

NH3 + H2O NH4 + OH
t
t
NH3

q r
Kb = antilog (pKb)

Kb q
4.75 5
Kb = 10 = 1.77 10 M
t rs OH NH3 + H2O NH4+ + OH

r
(M)
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)

0.10 0.20 0
t
pH
(M)


r
x +x +x

(M)
pKb = log (Kb) (7.34)
0.10 x 0.20 + x x
+
Kb= [NH4 ][OH ] / [NH3]

5
= (0.20 + x)(x) / (0.1 x) = 1.77 10
0.004 M t pH 9.7
Kb 0.1M 0.2 M

Kb pKb t
x

5
[OH ]= x = 0.88 10
+ 9
NH2NH2 + H2O NH2NH3 + OH
+ [H ]= 1.12 10
+
pH = log[H ] = 8.95
pH t

t t
Ka Kb

r Ka Kb s

+
[H ] = antilog (pH) = antilog (9.7)

10
= 1.67 10 t NH4+
210

r NH3 r r
NH4+(aq) + H2O(l) H3O+(aq) + NH3(aq) r r r
Ka = [H3O+][ NH3] / [NH4+] = 5.6 1010 r
NH3(aq) + H2O(l) NH4+(aq) + OH(aq) pK a + pK b = pK w = 14 (298K )

Kb =[ NH4+][ OH] / NH3 = 1.8 10-5

2 H2O(l) H3O+(aq) + OH(aq) 0.05 M q r pH
Kw = [H3O+][ OH ] = 1.0 1014 M r
Ka NH4+ r Kb, NH3 r sts
r r
r
Ka r Kb r
NH3
Ka K b = {[H3O+][ NH3] / [NH4+ ]} {[NH4+ ]
r
[ OH-] / [NH3]} +
NH3 + H2O NH4 + OH
= [H3O ][ OH ] = Kw
+

= (5.6 1010) (1.8 105) = 1.0 1014 M st

r r

r r
[OH ] = c = 0.05
2
Kb = 0.05 / (1 )

PP r
K = K1 K2 (3.35) r r
r
Ka Kb = Kw (7.36) Kb = c
2
or
5
= (1.77 10 / 0.05)
r r r = 0.018.
r
[OH ] = c a = 0.05 0.018 = 9.4 10 M.
4

r
r +
[H ] = Kw / [OH ] = 10
14
/ (9.4 10 )
4

11
r K w = K a K b = 1.06 10
11
r pH = log(1.06 10 ) = 10.97.
r
r
B(aq) + H2O(l) BH+(aq) + OH(aq) Ka Kb = Kw
Kb = [BH ][OH ] / [B]
+
r sts r NH3 Kb
r r r NH4 r r
+

r Ka = K w / K b = 10
14
/ 1.77 10
5

10
r [H+] = 5.64 10
r

Kb = [BH+][OH][H+] / [B][H+]

={[ OH][H+]}{[BH+] / [B][H+]}
= Kw / K a
Ka Kb = Kw r r
 211

qq st

H2X pH r

H2X(aq) H+(aq) + HX(aq)

HX(aq) H+(aq) + X2(aq)

r
H A

= {[H ][HX ]} / [H2X] (8.16)

+

= {[H+][X2-]} / [HX-] (8.17) HA

HA


H 2X

HA

H3PO4

H A

298 K P

HA

A HA

HF << HCl << HBr << HI

H2S, H2O

(Ka)
HA

H2CO3 HCO3
A

HPO2
4
H2PO4

CH4 < NH3 < H2O < HF

H2A
H2A, HA
A 2
qq st s

H2A s

H3O +

212

CH3COOH(aq) H+(aq) + CH3COO (aq) P

HAc(aq) H+ (aq) + Ac (aq)
NH3 + H2O NH4 + OH
+

Ka = [H ][Ac ] / [HAc]
+
+ 5
Kb = [NH4 ][OH ] / [NH3] = 1.77 10

+
[NH4 ] = [OH ] = x

H+
[NH3] = 0.10 x 0.10
2 5
x / 0.10 = 1.77 10
3
x = 1.33 10 = [OH ]
[H+] + 14
[H ] = Kw / [OH ] = 10 /
14 3 12
10 /(1.33 10 ) = 7.51 10
12
pH = log(7.5 10 ) = 11.12

25 mL 0.1M HCl 2.5

HCl 50 mL 0.1 M
5 mL NH3 2.5
75 mL
0.05 M 0.05 M
2.5 NH3
+
2.5 NH4
pH
NH3 + HCl NH4+ + Cl
HAc(aq) H (aq) + Ac (aq)
+
2.5 2.5 0 0
(M)

0.05 0 0.05
0 0 2.5 2.5
x
75 mL 2.5 NH4+
(M)
(0.033 M) 2.5
x +x +x
NH3 (0.033 M)
(M) NH3
0.05-x x 0.05+x +
NH4OH NH4 + OH
0.033M y y y
Ka= [H+][Ac ]/[H Ac] = {(0.05+x)(x)}/(0.05-x) +
y = [OH ] = [NH4 ]
Ka x << 0.05 75 mL
(0.05 + x) (0.05 x) 0.05 2.5 NH4 (0.033 M)
+

+
1.8 105 = (x) (0.05 + x) / (0.05 x) NH4
+
[NH4 ] = 0.033 + y
= x(0.05) / (0.05) = x = [H+] = 1.8 105M
pH = log(1.8 105) = 4.74 y [NH4OH] 0.033 M [NH4+]
0.033M.
P
0.10 M pH
+
Kb = [NH4 ][OH ] / [NH4OH]
5
50 mL 0.10 M HCl = y(0.033)/(0.033) = 1.77 10 M
5
25.0 mL pH y = 1.77 10 = [OH ]
+ 14 5 9
K b = 1.77 [H ] = 10 / 1.77 10 = 0.56 10
10
5
pH = 9.24
 213

NH4OH
pH H +

(Kb = 1.77 105)

H+

NH4Cl

pH 7

pH

Na+, K+, Ca2+, Ba2+

CH3COONH4 P

Cl , Br ,

NO3, ClO4 CH3COO + NH4+ + H2O CH3COOH +

NH4OH

pH 7 CH3COOH NH4OH

P
CH3COOH q CH3COO + H+


NH4OH r NH4+ + OH
(i)

H 2O q H+ + OH

CH3COONa

(ii)

s
s

NH4Cl,
pH

(iii)

pH = 7 + (pKa pKb) (7.38)
CH3COONH4 pH 7

pH 7
CH3COONa,

CH3COOH NaOH

t
pKa

CH3COONa(aq) CH3COO (aq)+ Na+(aq)

pKb

pH

OH

CH3COO (aq)+H2O(l) CH3COOH(aq)+OH (aq)

pH = 7 + [pKa pKb]

(Ka = 1.8 105) =7+ [4.76 4.75]

=7+ [0.01] = 7 + 0.005 = 7.005
OH

pH 7

t s

NH4OH pH
pH

HCl NH4Cl t
(Malfunctioning) t

NH4Cl(aq)


(aq) +Cl (aq) pH
214

I > 0.1 M
(Consmetic Formulation) II 0.01 < < 0.1 M
pH III < 0.01 M
pH

pH
pK a pK b P
P

pH, 4.75
P P
pH, 9.25 P BaSO4(s) Ba2+(aq) + SO42(aq),

P
q rs t
K = {[Ba2+][SO42]} / [BaSO4]
P P
Ksp = K[BaSO4] = [Ba2+][SO42] (7.39)
P Ksp
Ksp
298 K 1.1 1010

P
(Lattice Enthalpy)
P P
P 'S'
1.1 1010 = (S)(S) = S2 S = 1.05 105

P 1.05 105 mol L1



P P P

P (Zr4+)3
(Overcome)
(PO43)4 P

P 4
P
'S'

[Zr4+] = 3S [PO43] = 4S
Ksp = (3S) (4S) = 6912 (S)
3 4 7

S = {Ksp / (33 44)}1/7 = (Ksp / 6912)1/7

 215

298K qst s

qs q t Ksp s

'S'

MxXy(s) xMp+(aq) + yXq (aq)

( x p+ = y q)
r

Ksp = [Mp+]x[Xq ]y = (xS)x(yS)y (7.40)

=x .y .S x y (x + y)

S (x + y)
= Ksp / xx . yy
r S = (Ksp / xx . yy)1 / x + y (7.41)

Ksp Qsp

rr

Ksp= Qsp

(Dissolution)

298 K

A2X3

A2X3 Ksp
23
= 1.1 10

3+ 2
A2X3 2A + 3X
3+ 2 2 3 23
Ksp = [A ] [X ] = 1.1 10
S = A2X3,

3+ 2
[A ] = 2S; [X ] = 3S
2 3 5
r Ksp = (2S) (3S) = 108S
23
= 1.1 10
5 25
S = 1 10
5
S = 1.0 10 mol/L.

Ni (OH)2 AgCN

15
2.0 10

17
6 10
216

1
AgCN
+
Ag + CN

Ni (OH)2 r S mol L
+
Ksp = [Ag ][CN ] = 6 10
17
Ni2+ (S) OH 2S mol L1
Ni(OH)2 Ni
2+
+ 2OH
r OH r OH
(0.10 + 2S) mol L
1
2+ 2 15
Ksp = [Ni ][OH ] = 2 10
[Ag+] = S1, r [CN-] = S1 NaOH r 0.10 mol L1 r
15 2+ 2
Ksp = 2.0 10 = [Ni ] [OH ] = (S) (0.10 +
[Ni ] = S2, r [OH ] = 2S2
2+
2S)
2
2 17 9
S1 = 6 10 , S1 = 7.8 10 K sp 2S << 0.10
2 15 4
(S2)(2S2) = 2 10 , S2 = 0.58 10
r (0.10 + 2S) 0.10
AgCN Ni(OH)2 r r 2.0 1015 = S (0.10)2
13 2+
S = 2.0 10 M = [Ni ]


r pH
r r r r pH r
r
r r r r r
r r r r Ksp = Qsp r
Ksp = Qsp r r r Ksp = [M+] [X],
r r qs t q t s t
r Ksp = Qsp

r Qsp
r r (activities)
r rr HCI [X ] / [HX] = Ka / [H+]
r r r r r
r
r r r
P

r r r
P r
qs s q
r
s
P P
r [X ] / {[X ] +
r P [HX]} = f = Ka / (Ka + [H+]) r
r pH 'f' r pH
r S r
Ksp = [S] [f S] = S2 {Ka / (Ka + [H+])}
0.10 M NaOH Ni (OH)2 r
S = {Ksp ([H+] + Ka ) / Ka }1/2 (7.42)
Ni (OH)2
15
r S, [H ] pH r
+
2.0 10
r
 217

Kc

c d a b
aA+bB c C +d D K = [C] [D] /[A] [B]
c

Kp

Qc

Kc

(Ka)

(Kb)

pH (pH = -log[H+])

(pOH = log[OH ]) ; pKa = log[Ka] ; pKb =
log[Kb r pKw = log[Kw] pH +
pOH = pKw

(Ksp)

218

P P P P
q rs t s t t t s
pH r pH tt t r
pH tt t pH r s r
tr rr t
r t r pH tt
t pH r r
q pH q t r s r
t t r
t r t t r
pH t r pH t pH tt tr t
r r

Kc [SO2]= 0.60M,
[O2] = 0.82M [SO3] = 1.90M
2SO2(g) + O2(g) 2SO3(g)
105 Pa 40%

I2 (g) 2I (g)
Kp
Kc
(i) 2NOCl (g) 2NO (g) + Cl2 (g)
(ii) 2Cu(NO3)2 (s) 2CuO (s) + 4NO2 (g) + O2 (g)
(iii) CH3COOC2H5(aq) + H2O(l) CH3COOH (aq) + C2H5OH (aq)
(iv) Fe3+ (aq) + 3OH (aq) Fe(OH)3 (s)
(v) I2 (s) + 5F2 2IF5
Kp Kc
(i) 2NOCl (g) 2NO (g) + Cl2 (g); Kp= 1.8 102 at 500 K
(ii) CaCO3 (s) CaO(s) + CO2(g); Kp= 167 at 1073 K
 219

NO (g) + O3 (g) NO2 (g) + O2 (g) 1000K Kc = 6.3 1014

Kc

N2 O2

2N2 (g) + O2 (g) 2N2O (g)

10L 0.482 N 0.933 O
2 2
N2O Kc= 2.0 1037
Br2

2NO (g) + Br2 (g) 2NOBr (g)

0.087 NO 0.0437 Br2

0.0518 NOBr NO Br

2

2SO2(g) + O2(g) 2SO3 (g) 450K Kp= 2.0 1010 bar

Kc

HI(g) 0.2 atm HI(g)

0.04 atm Kp

2HI (g) H2 (g) + I2 (g)

500K 20L N2 1.57 H2 1.92 NH3 8.13

N (g) + 3H2 (g) 2NH3 (g) Kc

2

1.7 10 2

H2O CO 725 K 10L

40% t CO
H2O (g) + CO (g) H2 (g) + CO2 (g)

700K H2 (g) + I2 (g) 2HI (g) 54.8

HI(g) 700K
0.5 mol L HI(g)
1

H2(g) I2(g)
ICI, 0.78 M

2ICl (g) I2 (g) + Cl2 (g); Kc = 0.14

899 K KP 0.04 atm C2H6

220

4.0 atm C2H6

t
C2H6 (g) C2H4 (g) + H2 (g)
t
t
CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l)
(i) Qc
t
(ii) 293K 1.00 0.18 t
0.171 t
(iii) 0.5 1.0 293K r
0.214
437K PCl5
PCl5 0.5 101 mol L1 Kc 8.3 103
PCl3 Cl2

PCl5 (g) PCl3 (g) + Cl2(g)
t (II)
CO2
FeO (s) + CO (g) Fe (s) + CO2 (g); Kp = 0.265 atm at 1050K
1050K CO CO2

pCO= 1.4 atm = 0.80 atm
N2 (g) + 3H2 (g) 2NH3 (g) 500 K Kc =
0.061
3.0 mol L1 N2, 2.0 mol L1 H2 0.5 mol L1 NH3

BrCl
2BrCl (g) Br2 (g) + Cl2 (g)
500K Kc= 32 BrCl 3.3 103 mol L1

1127K 1 atm CO CO2
90.55% CO
C (s) + CO2 (g) 2CO (g)
Kc t
298K NO O2 NO2
NO (g) + O2 (g) NO2 (g)
G t
 221

f
G (NO2) = 52.0 kJ/mol

f
G (NO) = 87.0 kJ/mol

f
G (O2) = 0 kJ/mol

PCl5 (g) PCl3 (g) + Cl2 (g)

CaO (s) + CO2 (g) CaCO3 (s)
3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)

(i) COCl2 (g) CO (g) + Cl2 (g)

(ii) CH4 (g) + 2S2 (g) CS2 (g) + 2H2S (g)
(iii) CO2 (g) + C (s) 2CO (g)
(iv) 2H2 (g) + CO (g) CH3OH (g)
(v) CaCO3 (s) CaO (s) + CO2 (g)
(vi) 4 NH3 (g) + 5O2 (g) 4NO (g) + 6H2O(g)
1024K 1.6 105

H2(g) + Br2(g) 2HBr(g)

HBr 10.0 bar 1024K

CH4 (g) + H2O (g) CO (g) + 3H2 (g)

Kp

Kp

(i)

(ii)

(iii)

2H2(g) + CO (g) CH3OH (g)

H2

CH3OH

CO

CH3OH

473K PCl5 Kc 8.3 10-3

PCl5 (g) PCl3 (g) + Cl2 (g) H = 124.0 kJ mol1

r

222

Kc
Kc
(i) PCl5 (ii) (iii)
Kc

CO H2
CO
CO (g) + H2O (g) CO2 (g) + H2 (g)
400 C CO
r , H2 400C Kp= 10.1

Cl2 (g) 2Cl (g) Kc = 5 1039
Cl2 (g) + 2NO (g) 2NOCl (g) Kc = 3.7 108
Cl2 (g) + 2NO2 (g) 2NO2Cl (g) Kc = 1.8
25C 3O2 (g) 2O3 (g) Kc 2.0 1050
25C O2 1.6 102 O3
CO(g) + 3H2(g) CH4(g) + H2O(g) 1300K
CO 0.3 H2 0.01 H2O 0.02 CH4
Kc 3.90 CH4

P
HNO2, CN, HClO4 F , OH, S
2

H2O, BF3, H+ NH4+

HF, H2SO4 HCO 3

NH2, NH3 HCOO

P H2O, HCO3, HSO4 NH3

P
OH F H+ BCl3

3.8 103 M pH

pH, 3.76
HF, HCOOH HCN 298K 6.8 104, 1.8 104
4.8 109
 223

1.0 1010 0.05M

0.01M

H2S 9.1 10 8
0.1M HS

0.1 M HCl

H 2S 1.2 1013 S2

1.74 105 0.05 M

pH

0.01M (HA) pH, 4.15

pKa
pH

0.003 M HCl 0.005 M NaOH

0.002 M HBr 0.002 M KOH
pH

2 TlOH 2

0.3 Ca(OH)2 500 mL

0.3 NaOH 200 mL

13.6 M HCl 1mL

0.132 0.1M pH pKa

0.005M (C18H21NO3) pH 9.95

0.001M pH 7.7

0.05M pKa 4.74

0.01M 0.1M HCl

5.4 104 0.02M

NaOH 0.1M

pH

6.83 1.2
7.38 6.4
pH 6.8, 5.0, 4.2,
2.2 7.8 H +

298K 0.561 g, KOH t 200 mL pH,

298K Sr(OH)2 19.23 g/L

pH
224

1.32 105 0.05M

r pH r 0.01 M HCl r
r
(HCNO) 0.1M pH, 2.34 r
r r
4.5 104 r 0.04M
pH r r
0.02M pH 3.44 r

r
r r r
NaCl, KBr, NaCN, NH4NO3, NaNO2 r KF
1.35 103 0.1M r 0.1M
pH r
310K 2.7 1014 r pH
r
r pH r
0.2M Ca(OH)2 10 mL + 0.1M HCl 25 mL
0.01M H2SO4 10 mL + 0.01M Ca(OH)2 10 mL
0.1M H2SO4 10 mL + 0.1M KOH 10 mL
r
7.9 r r r r r
r r
Ag2CrO4 r AgBr r 1.1 1012 r 5.0 1013
rr r r r
0.002M r r r
r t Ksp = 7.4 108
6.46 105 r Ksp 2.5 1013

3.19 pH r r t
r r r r
r r
Ksp = 6.3 1018
r r r t
Ksp = 9.1 106
0.1M HCl r r r 1.0 1019 M
10 mL r 0.04M 5 mL r
r t FeSO4, MnCl2, ZnCl2, CdCl2.


5.7

ump.

n





u1,u2,u3, .un,

uav

u +u +..........u n
u av = 1 2

T1 T2

2
300 K q s

st




s


s st

t

s st
qr st
s q s

1 qr st
s

st
ss q s

II

aq.
1
mu 2 ,
2 HCl(g) + 10 aq. HCl.10 aq.
H = 69.01 kJ / mol
u 2

u12 +u 22 +..........u 2n
u2 (S-1) HCl(g) + 25 aq. HCl.25 aq.
n H = 72.03 kJ / mol

(S-2) HCl(g) + 40 aq. HCl.40 aq.
H = 72.79 kJ / mol

(S-3) HCl(g) + aq. HCl. aq.
(Root H = 74.85 kJ / mol
mean square speed) H


u rms = u 2
P
S-3 H

S-2
S-1
urms > uav > ump
HCl.25 aq. + 15 aq. HCl.40 aq.
H = [ 72.79 (72.03)]
kJ / mol = 0.76 kJ / mol
ump: uav :urms : : 1:1.128 : 1.224 H ( 0.76 kJ/mol)





6.5 r
6.6 r qs t


P

P 10 mol 10 mol



III

pH

pH,

Kb

6.6 P P

HA

HA + H2O
H3O + A

[H 3O + ] [A ]

Ka = [HA]

[HA]
[H 3O + ] = Ka [A ]
Pr

P r
r
P

q r
r


s P

q r P P r P q

[A ]

pK a pH log

[HA]

[A ]
pH = pK a log ( )

0K

[HA]

A ]

[
pH = pK a + log

[
HA]
(

0K

298 K

( 2)

[A ]

,
[HA]

[HA],

7.12.1.

[A ],

pKa, pKb

pH

IV

[ ]
pH = pK a + log
[ ] [ BH + ]
pK w pH= pK w pK a + log
-1 [A] [HA] [PP B]
pH = pKa log1


[ BH + ]
pH = pK a + log (4)
pH pK [ B]
a
pH q
pH

pKa pH
pKa 4.76 pKa pKa 9.25
9.25 pH

pH 4.76


st
(4)
[ r BH + ]
pOH = pK b + log (-3) [ BH + ]
[ B] pH = 9.25 + log
[ B]
pH pH
+ pOH =14 pH
pH + pOH = pKw pKa +
pKb = pKw (-3)