Date: 05/03/2018

Experiment No: 13
Experiment: pH determination by Gran titration theory.

Aims and objectives

 To understand different end-point detection methods used in acid base titrations.
 To become familiar with the techniques of gran titration for detection for detection of titration end
points.
 To become familiar with the use of pH electrode.
 To become familiar with the use of Microsoft excel spreadsheet and equations.

Introduction
In this experiment you will perform a potentiometric titration of a strong acid (HCl) with strong base (NaOH).
The data collected will be transformed using Gran function to increase the data and estimate the end point.
This technique is very powerful because it utilizes titration information away from the region of the end-point
where tittle apparent change is occurring in electrode response. To perform the calculation you need to use a
suitable spreadsheet / graphs such as excel.

Theory
Glass type pH electrodes give logarithmic signal response (in volts or millivolts) to hydrogen ion activity in
aqueous solutions, and thus a linear response to pH. Normally the signal in the pH meter is processed to read
pH units once a suitable calibration has been performed using buffer solution of known pH. This is often quite
tedious requiring adjustment of slope and constant controls to ensure that the transformation of the raw mV
data to pH is acceptable. However, the use of gran function to estimate end-points in potentiometric titrations
these tedious activities, and has the following advantages.

 It is not necessary to calibrate the pH meter since the change in electrode response during the titration
is used to estimate the end-point. The raw mV details used.
 Once the end-point is known, the electrode.
Gran’s method utilizes the mass balance condition for the titration reaction. The basis of the technique is the
formulation of the parameters (Gran function) that are directly proportional to the concentration of acid or base
present. Gran functions are thus linear and extrapolate to zero at the equivalence point. Consider the reaction
of HCl with NaOH (strong acid with strong base). We assume the reaction to be.
H3O++OH- ⇋ 2H2O

In this case, there are two regions of the titration curve for which we can derive useful Gran functions.
In the first region, V < Ve where V is the volume of NaOH added and Ve is the equivalence volume where
the amount of hydroxyl ion added equyals the amount of hydrogen ion present HCl is present excess. So
the solution is acidic.
The second region of interest is where V>Ve ; here all the HCl has been consumed. NaOH is excess and the
solution is basic.
When V<Ve the amount of hydroge ion nH+ at any volume is given by,
nH+ = nHCl(original) – nNaOH(added)
= V0[HCl] – V[NaOH] (2)
Where V0 is the original volume of HCl solution. At the equivalence volume the amounts of HCl and NaOH
are equal, therefore Ve [NaOH] = V0[HCl], by substitution, it is apparent that,
nH+ = Ve[NaOH] – V[NaOH]
= (Ve – V) [NaOH] (3)
it is also true that at any time during the titration in the region V<Ve
nH+ = [H3O+] (V0+V) (4)
Where (V0+V) is the total volume of the solution. If a potentiometric titration is carried out under conditions of
constant ionic strength. The potential of the cell (E) becomes a linear function of log [H3O+].
E = constant + k.log [H3O+] (5)
log [H3O+] = E/k – constant/k
[H3O+] = 10E/k / 10constant/k
by using (5),(4) and (3) we obtain,
nH+ = (V0+V) 10 [(E/k) – (constant/k) = (Ve-V)[NaOH]

nH+ = (V0+V) 10(E/k) = (Ve-V) [NaOH] ⨯ 10(constant/k) (6)

Because the right-hand side of (6) is linear function of the titrant volume V (which extrapolates to zero when
(V=Ve) and we can plot any function directly proportional to nH+ to obtain Ve, the constant [NaOH] and
10(constant/k) can be remove simplifying (6) to,

F1 = (V0+V) 10(E/k) (7)

Equation (7) is called a gran function and is denoted by the symbol F1. The right hand side contains only known
values; the exact volume of analyte V0 the titrant volume V, the cell potential E, and the electrode slope constant
k, (7) is linearly proportional to the amount of hydrogen ions in the solution (and thus the titrant volume), with
negative slope and a zero values at V = Ve .

A second Gran function F2 is derived for the region V > Ve in a similar manner. in this region OH- is in excess;
therefore the amount of OH- present is,

nOH- = nNaOH(added) – nHCl(original)

= (V – Ve) [NaOH] (8)

To obtain an expression of cell potential proportional to the amount of OH- present, we utilize the relationship
of [OH-] to [H3O+] via the equilibrium for the dissociation of water.

[OH-][H3O+] = ckw (9)

Thus the cell potential equation (5) can be written in terms of [OH-]
E = (constant + k log ckw) - log [OH-] (10)

This after taking antilogarithms and removing constant multiplies to

[OH-] µ 10 – E /k (11)

After the equivalence point, no further OH- will be consumed. Thus [OH-] becomes a function of the original
[NaOH] and a dilution factor introduced by the initial volume of HCl present and the volume of NaOH added.

[OH-] = (V – Ve) [NaOH] / (V0 + V)

[OH-] (V0 + V) = (V – Ve) [NaOH]

Finally, by removing the constant of initial [NaOH] and substituting in (11) we derive our second Gran function.

F2 = (V0 + V) 10 –E/k

Procedure

titration of HCl and NaOH

0.1 moldm-3 NaOH solution was prepared.0.1 moldm-3 HCl solution was prepared. 25.00 ml from 0.1 M HCl
solution and 25.00 ml deionized water was added to a 100 ml beaker. The burette was filled with 0.1 M NaOH
solution. The flask containing HCl was placed on a stirrer under the burette and the stirrer start gentles. The
pH electrode was placed in the solution that is not interfered with the stirring bar. The mV signal was
recorded. 0.5 ml aliquots of NaOH was added until total of 40.00 ml has been added. Addition of each aliquot
was followed and allowed the electrode response to stabilize. Then the mV value was recorded.

Titration of K2Cr207 and Feso4.(NH4)2SO4.6H2O

0.06 moldm-3 Fe+2 solution was prepared. 0.01 moldm-3 K2Cr2O7 solution was prepared.25.00 cm-3 of the
ferrous solution was pipetted out into a dry 250cm-3 beaker. 20.00 cm-3 0f 5M H2SO4 and 50.00 cm-3 of water
was added. Platinum electrode was dipped into the solution. The electrode was coupled with a SCE. The
electrode was connected to the potentiometer. The burette was filled with 0.01 K 2Cr2O7 solution. The flask
containing Fe+2 was placed on a stirrer under the burette and the stirrer start gentles. The pt electrode and
SCE was placed in the solution that is not interfered with the stirring bar. The mV signal was recorded. 0.5 ml
aliquots of K2Cr2O7 was added until total of 40.00 ml has been added. Addition of each aliquot was followed
and allowed the electrode response to stabilize. Then the mV value was recorded.
Calculations
volume of
volume of NaOH/cm- volume of
volume of NaOH/cm-3 NaOH/cm-4 5
NaOH/cm-6
initial 325
0.5 329 9235008 6.76502E-05
1 326 8047018 7.75443E-05
1.5 326 7879372 7.90355E-05
2 325 7416558 8.37316E-05
2.5 325 7255329 8.52821E-05
4.5 314 4303163 0.000140536
5 313 4037521 0.000148606
5.5 313 3936582 0.000151083
6 313 3835644 0.00015356
6.5 312 3591760 0.000162246
7 312 3494686 0.000164822
7.5 311 3267567 0.000174059
8 311 3174208 0.000176737
8.5 310 2962929 0.000186555
9 309 2763173 0.000196875
9.5 308 2574368 0.000207721
10 307 2395968 0.000219118
10.5 306 2227454 0.000231093
11 305 2068329 0.000243675
11.5 304 1918122 0.000256892
12 303 1776383 0.000270775
12.5 302 1642684 0.000285356
13 301 1516618 0.000300669
13.5 300 1397795 0.000316749
14 299 1285847 0.000333632
14.5 298 1180421 0.000351358
15 297 1081181 0.000369966
15.5 296 987808.5 0.000389499
16 295 900000 0.00041
16.5 294 817466.1 0.000431516
17 293 739931.8 0.000454096
17.5 292 667135.1 0.000477789
18 290 575906.9 0.000522654
18.5 288 494617.3 0.000571654
19 286 422288.1 0.000625166
19.5 284 358032.1 0.000683598
20 281 289522.2 0.000777142
20.5 279 241005 0.000849567
21 277 198141.4 0.00092863
21.5 274 154218.3 0.001055322
22 271 117582.2 0.001199161
 22.5 267 83823.1 0.001416674
23 263 57366.34 0.001673455
23.5 259 36806.27 0.001976566
24 251 17957.14 0.002728719
24.5 244 6832.242 0.00362253
25 229 0 0.006570737
25.5 203 -1379.27 0.018306841
26 60.1 -10.4386 4.885692262
26.5 -94.3 -0.03783 2042.266031
27 -150 -0.00574 18129.09918
27.5 -185 -0.00183 71738.53834
28 -202 -0.00113 140606.2686
28.5 -220 -0.00065 286528.1801
29 -228 -0.00055 395185.0798
29.5 -236 -0.00045 545000
30 -243 -0.00038 722781.0494
30.5 -251 -0.00031 996621.5444
31 -254 -0.0003 1130505.743
31.5 -257 -0.00029 1282273.453
32 -259 -0.00029 1398638.131
32.5 -260 -0.00029 1467058.749
33 -263 -0.00028 1663623.752
33.5 -265 -0.00027 1814183.822
34 -266 -0.00028 1902508.422
34.5 -268 -0.00027 2074387.31
35 -269 -0.00028 2175070.23
35.5 -270 -0.00028 2280481.54
36 -271 -0.00028 2390838.133
36.5 -272 -0.00028 2506366.674
37 -273 -0.00028 2627304.04
37.5 -274 -0.00028 2753897.767
38 -275 -0.00028 2886406.532
38.5 -276 -0.00028 3025100.637
39 -277 -0.00028 3170262.534
39.5 -277 -0.00029 3195030.21
40 -278 -0.00029 3347940.75
20.9025974 97.01025641 1343256 600915.7843
 mV vs NaOH
400

300

200
average potential /mV

100

0
0 10 20 30 40 50 60 70 80 90
-100

-200

-300

-400
volume of NaOH/cm-3

volume of NaOH/cm-3 volume of NaOH/cm-4

F1 vs NaOH y = -69011x + 4E+06

R² = 0.5536
10000000

8000000

6000000

4000000

2000000

0
0 10 20 30 40 50 60 70 80 90

-2000000

Series1 Series2 Series3 Linear (Series2) Linear (Series2)

 F2 vs NaOH y = 33985x - 799659
R² = 0.5869
4000000

3500000

3000000

2500000

2000000

1500000

1000000

500000

0
0 10 20 30 40 50 60 70 80 90
-500000

-1000000

Series1 Series2 Series3 Linear (Series2) Linear (Series2)

F1,F2 vs NaOH y = -73196x + 4E+06

R² = 0.6013
10000000

8000000

6000000

4000000

2000000

0
0 10 20 30 40 50 60 70 80 90

-2000000

-4000000

volume of NaOH/cm-6 initial Linear (volume of NaOH/cm-6) Linear ()

Discussion
Pre lab questions
1). How would you modify this experiment to determine the dissociation constant of a weak acid or base?
Hence, derive an equation used to plot a gran plot for a weak acid HA (dissociation constant – Ka) – strong
base titration.
Consider the titration of a weak acid, HA

HA ⇋ H+ + A-

[H+ ] 𝛾H+ [A− ]𝛾A−

Ka = (1)
[HA]γHA

It will be necessary to include activity coefficient in this discussion because a pH electrode respond to
hydrogen ion activity, not concentration.

[A] = moles of OH- delivered/ total volume

vb[NaOH]
=
va+vb
[HA] = (original moles of HA – moles of OH)/total volume
va[HA]−vb[NaOH]
=
va+vb
Substitution of these values of [A-] and [HA] into the equilibrium constant gives,
[H+ ] 𝛾H+ +𝑣𝑏[NaOH]𝛾A−
Ka =
(𝑣𝑎[HA]−vb[NaOH]γHA
Which can be rearranged to,
va[HA]−vbFb
Vb[H+]𝛾H+ = 𝛾[HA] 𝛾[A-]ka =
Fb
va[HA]−vb[NaOH] vb[AH]
Since [H+] 𝛾H+ = 10 – pH, and = – Vb = V e - Vb
[NaOH] [NaOH]
Therefore equation 2 can be written as,
𝛾HA
Vb 10-pH = – ka (Ve – Vb)
𝛾A
𝛾HA
A graph of Vb.10-pH vs Vb clled a grant plot. If = is constant, the graph is a straight line with a slope of -
𝛾A
𝛾HA
ka and an x-intercept of Ve.
𝛾A

2). List down the application of grant titrations in industry and environmental chemistry.
To measure alkalinities and acidities of low-pH, low-ionic strength natural waters. It is appropriate to be used
when the sample concentration is very mall and when there are coloured compounds present in the medium.
Titrations that utilize measurement of pH have endpoints that can be determined by first and second
derivatives. However, a Gran plot can also be used. The power in utilize a Gran plot instead of the first and
second derivative lies in the fact that you do not need to pass the equivalence point to obtain an accurate
value. Gran’s method is applicable to potentiometric acid-base, redox, precipitation, and complex formation
titrations.