1&2

Potentiometric Determination of F
-
and H
+
Experiment 1 and 2
Barba, Biadomang, Dulos --- Cua, Narciso, Pilar
Saturday, August 13, 2011
Potentiometry
Electroanalytical chemistry
Potential is measured under
conditions of no current
ow
Measured potential
Determine analytical
quantity of interest of
[analyte]
Generally the
concentration of some
component of the analyte
solution
Potentiometry
Potential the develops in the electrochemical cell is the result of
the free energy change that would occur if the chemical
phenomena were to proceed until the equilibrium condition has
been satised
Potentiometric Measurement System
Potentiometer
Analyte solution
2 electrodes
Reference
Ind of ions in the soln and
T
Indicator
Produces potential related
to [analyte]
Types: membrane &
metallic
Membrane: Ion Selective Electrodes
Enables selective detection of ions in presence of multitude of
other substances
Characteristics:
Low solubility-solids, semi-solids, polymers
Some electrical conductivity
Selective! :)
Common ISEs
pH electrode
contains a thin glass membrane that responds to the H+
concentration in a solution
Fluoride-Ion Selective E
Frant & Ross
Selectively binds F- into both of its surfaces
Exterior surface: contact with the analyte solution
Interior surface with the uoride standard solution
(reference electrode solution)
Fluoride Ion Selective Electrode
Difference in the activity of
F- in the analyte solution
and in the membranes
interior solutions
------>Potential difference
LaF
3
= active membrane
Doped with Eu(II)
Electrical resistance
and ion charge
transport
Create lattice vacancies
LaF
3

(s)
+ F
-
(aq)
LaF
4(s)
-
pH Electrode
Combination
Glass electrode
Reference electrode
pH changes outside the solution
Nernst Equation
H
+
+ Na
+
Glass
-
H
+
Glass
-
+ Na
+
Ag/AgCl | HCl | Glass||Probed Solution | Ref Electrode
Alkaline and Acid Error
Alkaline
Absorb alkaline ions
Replace H+ ion outer gel
layer of glass membrane
pH value lower than
actual pH
Noticeable at pH 9-10
Acid
Absorb acid molecules
Decrease the activity of
hydrogen ions
pH higher than actual
pH
Toothpaste
Paste or gel used to clean
and maintain aesthetics and
health of teeth
Removes plaque & tartar
Suppresses halitosis
Unpleasant odor
exhaled in breathing
Delivers active
ingredients
Fluoride and xylitol
Active Ingredients
Xylitol
Tooth friendly non-fermentable sugar alcohol
Dental caries prevention
Fluoride
Most popular active ingredient of toothpaste
Formation of dental enamels and bonds
NaF: most common source
1000-1100 ppm (US), 1450 ppm (UK)
Feminine Wash
Normal pH: 3.8 to 4.5
Lactobacillus gasseri
Glycogen to lactic acid
Action
Cleanse
Re-balance pH
Objectives
Experiment 1
To use direct calibration
method and SAM to
potentiometrically
determine the
concentration of F- in
several toothpaste
samples
Experiment 2
To use direct calibration
method and SAM to
potentiometrically
determine the
concentration of H+ in
several feminine wash
samples
Standard
Calibration
Method
Standard Calibration Method
Calibration: established a relationship between signals
measured and known concentrations of analyte
SCM: uses a series of standard covering the appropriated
concentration range
Signals measured are directly related to the concentration of
the standard
Standard Calibration Method
Accounts for constants that may vary in the experiment
Signals from the analyte are directly compared against those
from the standard through the calibration curve
Disadvantages for SCM
Activity, not concentration should be measured
Does not mimic the natural environment of the analyte
Time-consuming
Standard
Addition
Method
Standard Addition Method
Addition (spiking) of one
or more increments of
standard analyte solution
Potential recorded before
and after
Assumptions
No change in ionic strength
Activity coefcient
No signicant alteration of
junction potential
!"#$%&'$()*+
,$%&'$()*+
Activity Coefcient
Function of ionic strength
Ration of relative
concentration of analyte to
total ionic strength
Advantages
Time
Matrix effects
Natural producs
Direct sampling
Information about samples
Precision
1.1% deviation
Working Equation
Patterned with the Nernst
Equation
Substitution & Rearrangement
Blank Correction
Working Equation
Methodology
Proper Usage of Potentiometer
Toothpaste
Feminine Wash
Reminders
Stir/Agitate the solutions while/before measuring its
potential
Using a magnetic stirrer: use insulation between container
and hot plate
Wash the electrode
Kleenex!
Potentiometric
Determination of Fluoride
in Toothpaste
Direct Calibration Method
! "#$%&'(&)*(+
,%#+-./+0&%+1"+
.2+3345+
! 67*$"27#+(&%%&'*89+2&+$7.''+
! /7:&%*;9+(.<+92("+$7.''+
62&%9+*<+)7.'=(+
(&<2.*<9%+
! >44+))?+
,*7:29+*<+>4+?7+
8&7:?92%*(+@.'A+
Standard Preparation
TISAB Preparation
- acld Lo waLer" rule
230ml d.P
2
C ln
300 ml beaker
- ComponenL of aceLaLe buer
- keeps pP ln ranae
+28.3ml alaclal
aceuc acld
- lonlc sLrenaLh buerlna
- Mlnlmlze llquld [uncuon poLenual
+29a naCl
- Chelauna aaenL
+2a 1,2-Lu1A
TISAB Preparation
- revenL LemperaLure chanaes
upon addluon of base
Sur and cool ln
waLer baLh
- Ad[usL pP Lo 3.3-3.3
Slowlv add 6M
naCP (~62ml)
- ln 300 ml volumeLrlc ask
ulluLe Lo mark
Measurement of Standard Solution
! "#$%&'
()*#'+,-./'0'()*#'
123
(
4'
! 56$7896':;<6%=$#'
! >$?<'@;9'7<$"#6'96$1?%A'
,**6976'B-'
6#6C<9;16'
! /8""#67';%'<D6'6#6C<9;16'789@$C6'
?%<9;18C6'699;97'
,**6976'"6@;96'
7=99?%A'
! 5?%?*?E6'7;#8=;%'D6$=%A''
.11'=7786'"6<F66%'
"6$&69'$%1'7=9969'
!"#$"%&"'(")*+,-+.-"
/0")'1%2',"
3 45+)%.5"6'*5,2+1"
!"%,21"7#$"%&"
3 8%9915)"',"*:5"515;*.'-5"
)%.(+;5"<,*.'-%;5"5..'.)"
=>>5.)5"95('.5"
)2..<,?"
3 4<,<><@5")'1%2',":5+2,?"" A--"2))%5"95*B55,"
95+C5."+,-")2..5."
Measurement of Standard Solution
Construction of Calibration Curve
+ 30 ul sLandard
l- soluuon and
measure poLenual
8epeaL procedure
unul 230 uL
(6 readlnas ln all)
ConsLrucL
callbrauon curve:
L vs loa[l]
Sample Preparation and Measurement
!"#$%&'$&
())(%*+,("&
,+-*."&#/&01-.&
2"+3"4&
5#,,).6"&#/&
,-+..&+-)7/(&
)8&9+("4&
:4+/,8"4&()&
01-.&6).&;+,3&
<7+/=(+=6".>&
+/?&?#.7("&
:+3"&0-.@'-.&
)8&,).7=)/&A&
+??&B0&-.&
:CDEFA&?#.7("&#/&
01-.&6).&;+,3&
G"+,74"&
*)("/=+.&&
!"#$%"#&'(&
)'')*+,-).&
-'#/0'1&)'&
!2"#&3'#&
4,-5&
6&7!"#&
89:;<=&">?=&
@>#/).&)'&
",A5&
B.,-/A.&
+').10,#&
6&-),1@,A@&
C&&>1&!2/#&
>1DA.".1)-&
E/10#&
7!2/#F&
B.,-/A.&
+').10,#&
,G.A&.,D*&
6&
Potentiometric Determination
of Hydrogen Ion in Feminine
Wash
Standard Calibration Metod
10.00 mL feminine wash + 0.5
M KCl
Standard hydrogen solutions Standard hydrogen solutions
KCl, relieve junction potential
1.00 x 10
-1
M to 1.00 x 10
-7
M with
HCl + 0.5M KCl
HCl is a strong acid, full
dissociate
Standard Calibration Metod
Calibration Curve
!
!"#$$!!"!#$%&'!
! !
!
!!
!"
!!!"!!!
!"# !
!
!
!
!
!" !! !!"# !
!
!
!
!
!
!"#$$!!"!#$%&'!
! !
!
!!
!"
!!!"!!!
!"!
10 mL
sample
0.10 mL 10
-1
M
[H+] solution
E
Results
Calculations
Data
Graphs
F
-
Ions in Toothpaste
Preparation of Standard F- Solutions
and Samples
Toothpaste Sample Weight (grams)
Colgate 1.0378
Happee 1.0005
Beam 1.0006
Vstd (uL) Fluoride (ppm) Fluoride (uM)
0 0.0000 0.0000
50 0.5024 26.422
100 1.0038 52.832
150 1.5042 79.168
200 2.0036 105.45
250 2.5020 131.68
Vstd (uL) E (mV)
0 78
50 3
100 -17
150 -27
200 -34
250 -42
Determination of Analyte
Concentration
Toothpaste Sample Fluoride (uM) Fluoride (ppm)
Colgate 97.6004 1.8542
Beam 37.7652 0.7175
Happee 47.0167 0.8932
Vstd (uL) Colgate Beam Happee
0 0.1884 0.1884 0.1884
50 0.2548 0.2843 0.2843
100 0.2872 0.4291 0.3575
150 0.3481 0.5394 0.4834
200 0.4067 0.6303 0.5859
250 0.4752 0.7637 0.6600
SAM Plot
Response vs Volume of Standard
Toothpaste
Sample
Correlation Slope Cunk
Colgate
Beam
Happee
0.9667 3.964x10^-4 2522.7043
0.9262 5.152x10^-4 1940.9938
0.9412 4.895x10^-4 2042.9009
Percentage Errors
Toothpaste
Samples
Toothpaste
Samples
DCM
(ppm)
SAM
(ppm)
Theol
ppm
% Error % Error
DCM
(ppm)
SAM
(ppm)
Theol
ppm
DC SA
Colgate
Beam
Happee
1.8542 2522.7043 1450 ~ 73.97
0.7175 1940.9938 1500 ~ 29.33
0.8932 2042.9009
No Known
Value
n/a n/a
H
+
Ions in Feminine Wash
Preparation of Standard H+ and
0.5M KCl Solutions
0.1 M HCl Solution
0.5 M KCl Solution
[H+] (M) log [H+] E (V)
1.00E-01 -1 0.3419
1.00E-02 -2 0.2805
1.00E-03 -3 0.1998
1.00E-04 -4 -0.0282
1.00E-05 -5 -0.0769
1.00E-06 -6 -0.0803
1.00E-07 -7 -0.0866
[H+] (M) log [H+] E (V)
1.00E-01 -1 0.3419
1.00E-02 -2 0.2805
1.00E-03 -3 0.1998
1.00E-05 -5 -0.0769
1.00E-06 -6 -0.0803
1.00E-07 -7 -0.0866
r 0.935372094
Slope 0.081564286
y-intercept 0.404857143
r 0.966049627
Slope 0.081564286
y-intercept 0.422657143
v = 0.0816x + 0.4227
8 = 0.93323
-0.2
-0.1
0
0.1
0.2
0.3
0.4
-8 -7 -6 -3 -4 -3 -2 -1 0
!
"
#
$
%
&'()*+,%
!"#$%-.%&'()*+,%
SLock SLandard PCl Soluuon Llnear (SLock SLandard PCl Soluuon)
Calculations for DCM
Sample
Solution E(V) log[H+] [H+] (M) pH
Theo
pH
Percent
error (%)
Gynepro 0.036 -4.74052 1.81752E-05 4.74 5 5.189596
pH care 0.0856 -4.13241 7.37206E-05 4.13 5 17.35178
pH care
( p u r e
a n d
fresh)
0.0934 -4.03678 9.18796E-05 4.04 5 19.26438
E (V) Sample Addition Value
Vstd (L) pH Care (pure
and fresh)
Gynepro pH Care (pure
and fresh)
Gynepro
0.0000 0.0889 0.0394 0.5000 0.5000
0.0001 0.1491 0.0546 2.741 0.7695
0.0002 0.1855 0.067 7.6744 1.0942
0.0003 0.2067 0.0788 13.9903 1.5298
0.0004 0.2195 0.104 20.1197 3.1221
0.0005 0.2297 0.1149 26.8867 4.2554
0.0006 0.2385 0.1256 34.5372 5.7675
0.0007 0.2451 0.1355 41.6929 7.6422
0.0008 0.2509 0.1457 49.2071 10.2125
0.0009 0.2556 0.156 56.2995 13.6856
0.001 0.2599 0.1666 63.6907 18.4959
Sample r R
2
Slope y-int x-int [H+]
pH Care
(pure
and
fresh)
0.9958 0.9916 65873.45 -4.09 -6.21E-05 1.52E-05
Gynepro 0.9390 0.8817 16715.41 -2.26 -13.52E-05 5.98E-05
Sample
Solution
Concentration
[H+] (M) pH
Theoretical
pH
Percent
error (%)
pH Care (pure
and fresh)
1.51806E-05 4.82 5 3.625792
Gynepro 5.9825E-05 4.22 5 15.53766
!"#"$%&'()"*"+,-&''"
./"#"-,001%0"
!"#"1$'1%)"*"2,2$"
./"#"-,&&1$'"
*1%,--"
*%,--"
%,--"
1%,--"
2%,--"
(%,--"
+%,--"
%%,--"
$%,--"
-,----" -,---2" -,---+" -,---$" -,---&" -,--1-"
!
"
#
$
%
&
#
"
'
(#)*'+,-'
.)/&*/0*'1**23%&'45%)#'%6'$7'8/0"'/&*'9:&"$0%'
34"5678"93:78"6;<"=78>?@" A!;837B"
CD;867"934"5678"93:78"6;<"=78>?@@" CD;867"9A!;837B@"
Calculations for SAM
y = 65873x - 4.0877
R! = 0.9916
y = 16715x - 2.26
R! = 0.8817
[H+] = 1/slope = 1/ 65873 = 1.52E-05
[H+] = 1/slope = 1/ 16715= 5.98E-05
pH = 4.82
pH = 4.22
%error = 3.625792%
%error = 15.53766%
Error Analysis
37.77% error: 0.0592 vs 0.081564286
SAM: Less error
pH range 4-5 --- pH range 3.8-4.5
Theoretical pH = 5
KCl
Non-carbon dioxide free water
pH meter
Inconsistent temperature

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