Fundamentals of Analytical Chemistry: 8th ed.

Chapter 21

Chapter 21

21-1 (a) An indicator electrode is an electrode used in potentiometry that responds to

variations in the activity of an analyte ion or molecule.

(b) A reference electrode is an electrode whose potential is known, constant and

independent of the type of solution in which it is immersed.

(c) An electrode of the first kind is a metal electrode that responds to the activity of its

cation in solution.

(d) An electrode of the second kind is a metal electrode that is used to determine the

concentration of an anion that forms a precipitate or a stable complex with the cation of

the electrode metal.

21-2 (a) A liquid junction potential is the potential that develops across the interface between

two solutions having different electrolyte compositions.

(b) A boundary potential is the potential that develops across an ion-sensitive membrane

when the two side of the membrane are bathed in solutions having different

concentrations of the ion to which the membrane is sensitive.

(c) The asymmetry potential is a potential that develops across an ion-sensitive membrane

when the concentrations of the ion are the same on either side of the membrane. This

potential arises from dissimilarities between the inner and outer surface of the membrane.

21-3 (a) An electrode of the first kind for Hg(II) would take the form

Hg2+(x M)Hg
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

(b) An electrode of the second kind for EDTA would take the form

HgY2- (y M), Y4- (x M)Hg

where a small and fixed amount of HgY2- is introduced into the analyte solution. Here

the potential of the mercury electrode is given by

21-4 For the process

The potential E should be linearly related to pM. A Nernstian response occurs where the

slope of the plot of E versus pM is -0.0592/n.

21-5 The potential arises from the difference in positions of dissociation equilibria on each of

the two surfaces. These equilibria are described by

The surface exposed to the solution having the higher H+ concentration becomes positive

with respect to the other surface. This charge difference, or potential, serves as the
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

analytical parameter when the pH of the solution on one side of the membrane is held

constant.

21-6 In order for a glass membrane to be pH sensitive, it is necessary that the two surfaces are

hydrated so that the equilibrium shown in Problem 21-5 can be established.

21-7 Uncertainties include (1) the acid error in highly acidic solutions, (2) the alkaline error in

strongly basic solutions, (3) the error that arises when the ionic strength of the calibration

standards differs from that of the analyte solution, (4) uncertainties in the pH of the

standard buffers, (5) nonreproducible junction potentials with solutions of low ionic

strength and (6) dehydration of the working surface.

21-8 Owing to variables that cannot be controlled, it is necessary to calibrate the response of

the membrane against one or more standards. It must then be assumed that the junction

potential associated with the external reference electrode does not change when the

standard is replaced by the test solution. The uncertainty associated with this assumption

translates into uncertainties in the second decimal place of the measured p-value.

21-9 The alkaline error arises when a glass electrode is employed to measure the pH of

solutions having pH values in the 10 to 12 range or greater. In the presence of alkali ions,

the glass surface becomes responsive to not only hydrogen ions but also alkali metal ions.

Measured pH values are low as a result.

21-10 A gas-sensing probe functions by permitting the gas to penetrate a hydrophobic

membrane and altering the composition of liquid on the inner side of the membrane. The

changes are registered by an indicator/reference electrode pair in contact with the inner
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

solution. Thus, there is no direct contact between the electrodes and the test solution as

there is with membrane electrodes.

21-11 (a) The asymmetry potential in a membrane arises from differences in the composition or

structure of the inner and outer surfaces. These differences may arise from contamination

of one of the surfaces, wear and abrasion and/or strains set up during manufacturing.

(b) The boundary potential for a membrane electrode is a potential that develops when

the membrane separates two solutions that have different concentrations of a cation or an

anion that the membrane binds selectively. For an aqueous solution, the following

equilibria develop when the membrane is positioned between two solutions of A+:

where the subscripts refer to the two sides of the membrane. A potential develops across

this membrane if one of these equilibria proceeds further to the right than the other, and

this potential is the boundary potential. For example, if the concentration of A+ is greater

in solution 1 than in solution 2, the negative charge on side 1 of the membrane will be

less than that of side 2 because the equilibrium on side 1 will lie further to the left. Thus,

a greater fraction of the negative charge on side 1 will be neutralized by A+.

(c) The junction potential in a glass/calomel electrode system develops at the interface

between the saturated KCl solution in the salt bridge and the sample solution. It is caused

by charge separation created by the differences in the rates at which ions migrate across

the interface.

(d) The membrane in a solid-state electrode for F- is crystalline LaF3, which when
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

immersed in aqueous solution, dissociates according to the equation

Thus, the boundary potential develops across this membrane when it separates two

solutions of F- ion concentration. The source of this potential is the same as described in

Problem 20-11(b).

21-12 The direct potentiometric measurement of pH provides a measure of the equilibrium

concentration of hydronium ions in the sample. A potentiometric titration provides

information on the amount of reactive protons, both ionized and nonionized, in the

sample.

21-13 Potentiometric titrations offer many advantages over direct potentiometry including (1)

yielding equivalence point data that are independent of Ecell and free of uncertainties

involving the junction potential, (2) electrode fouling and non-Nernstian behavior are not

as serious, (3) the reference electrode potential does not need to be known and (4) the

result is analyte concentration even though the electrode responds to activity, thus ionic

strengths are not important.

21-14 The “operational definition of pH” is based on the direct calibration of the meter with

carefully prescribed standard buffers followed by potentiometric determination of the pH

of unknown solutions. For example, if immerses one glass/reference electrode pair in a

standard buffer, we would write the relationship below

where ES is the cell potential when the electrodes are immersed in the buffer. Similarly,
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

if the cell potential is EU when the electrodes are immersed in a solution of unknown pH,

we would write

Subtracting the two relationships, we find

The last relationship has been adopted throughout the world as the operational definition

of pH. This definition ensures that pH measurements can be easily duplicated at various

times and in various laboratories.

21-15

(a)

When [IO3-] = 1.00, EAg is equal to for the reduction of AgIO3, that is,

(b) SCEIO3- (x M), AgIO3 (sat’d)Ag

(c)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

(d)

21-16 Proceeding as in the previous solution, we write

(a)

When [I-] = 1.00, E becomes and

(b) SCEI- (x M), PbI2 (s)Pb

(c)

(d)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

21-17 (a) SCESCN- (x M), AgSCN (sat’d)Ag

(b) SCEI- (x M), AgI (sat’d)Ag

(c) SCESO3- (x M), Ag2SO3 (sat’d)Ag

(d) SCEPO43- (x M), Ag3PO4 (sat’d)Ag

21-18 (a)

To obtain we proceed as in Problem 21-16(a). Thus,

Then we proceed as in Problem 21-16(c) and write

(b)

(c)

(d)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

21-19 (a)

(b)

(c)

(d)

21-20 SCEAg2CrO4 (sat’d), CrO42- (x M)Ag

Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

21-21 Substituting into Equation 21-22 gives

(a)

(b)

(c) For part (a),

Proceeding in the same way for part (b) we obtain

21-22
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

21-23 For all additions, we calculate

Pre-equivalence point region

The results are shown in the spreadsheet for this problem.

Equivalence point

Here [Ag+] = [SeCN–] = Ksp we use the Nernst equation to calculate EAg and then

obtain Ecell as before. The result is shown in cell D22 of the spreadsheet.

Post equivalence point region

The Ecell values are shown in column D of the spreadsheet.

First- and second-derivative plots

The calculations for the first- and second-derivative plots follow the method shown in

Applications of Microsoft Excel in Analytical Chemistry, Chapter 7 and in Table 21-4.

The resulting plots along with the titration curve follows.

Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

A B C D E F G H I J K L
1 21-23 Titration of 50.00 mL of 0.0800 M KSeCN with 0.1000 M AgNO 3
2 E0 for Ag+  Ag, V 0.799
3 Ksp for AgSeCN 4.20E-16AgSeCN(s)  Ag+ + SeCN-
4 ESCE, V 0.244
5 Initial conc. KSeCN 0.0800
6 Conc. AgNO3 0.1000
7 Initial volume, mL 50.00 First Derivative Second Derivative
8 Vol. AgNO3, mL [SeCN-] [Ag+] EAg vs. SCE, V Midpt. Vol. E Vol E/V Midpt. Vol. V Vol. E/V2
9 5.00 0.0636 6.60E-15 -0.282
10 15.00 0.0385 1.09E-14 -0.269 10.00 0.013 10.00 0.001
11 25.00 0.0200 2.10E-14 -0.252 20.00 0.017 10.00 0.002 15.00 0.0004 10.00 0.000
12 30.00 0.0125 3.36E-14 -0.240 27.50 0.012 5.00 0.002 23.75 0.0007 7.50 0.000
13 35.00 0.0059 7.14E-14 -0.221 32.50 0.019 5.00 0.004 30.00 0.0015 5.00 0.000
14 39.00 0.0011 3.74E-13 -0.178 37.00 0.042 4.00 0.011 34.75 0.0067 4.50 0.001
15 39.50 5.59E-04 7.52E-13 -0.160 39.25 0.018 0.50 0.036 38.13 0.0252 2.25 0.011
16 39.60 4.46E-04 9.41E-13 -0.155 39.55 0.006 0.10 0.057 39.40 0.0217 0.30 0.072
17 39.70 3.34E-04 1.26E-12 -0.147 39.65 0.007 0.10 0.074 39.60 0.0165 0.10 0.165
18 39.80 2.23E-04 1.89E-12 -0.137 39.75 0.010 0.10 0.104 39.70 0.0302 0.10 0.302
19 39.90 1.11E-04 3.78E-12 -0.119 39.85 0.018 0.10 0.178 39.80 0.0737 0.10 0.737
20 39.95 5.56E-05 7.56E-12 -0.101 39.93 0.018 0.05 0.356 39.89 0.1776 0.08 2.368
21 39.99 1.11E-05 3.78E-11 -0.060 39.97 0.041 0.04 1.031 39.95 0.6758 0.05 15.017
22 40.00 2.05E-08 0.101 40.00 0.161 0.01 16.132 39.98 15.1004 0.03 604.016
23 40.01 1.11E-05 0.263 40.01 0.161 0.01 16.131 40.00 -0.0006 0.01 -0.057
24 40.05 5.55E-05 0.304 40.03 0.041 0.04 1.031 40.02 -15.1004 0.03 -604.016
25 40.10 1.11E-04 0.322 40.08 0.018 0.05 0.355 40.05 -0.6758 0.05 -15.017
26 40.20 2.22E-04 0.339 40.15 0.018 0.10 0.177 40.11 -0.1776 0.08 -2.368
27 40.30 3.32E-04 0.350 40.25 0.010 0.10 0.104 40.20 -0.0737 0.10 -0.737
28 40.40 4.42E-04 0.357 40.35 0.007 0.10 0.073 40.30 -0.0302 0.10 -0.302
29 40.50 5.52E-04 0.363 40.45 0.006 0.10 0.057 40.40 -0.0165 0.10 -0.165
30 41.00 1.10E-03 0.380 40.75 0.018 0.50 0.035 40.60 -0.0217 0.30 -0.072
31 45.00 5.26E-03 0.421 43.00 0.040 4.00 0.010 41.88 -0.0252 2.25 -0.011
32 50.00 1.00E-02 0.437 47.50 0.016 5.00 0.003 45.25 -0.0067 4.50 -0.001
33 55.00 1.43E-02 0.446 52.50 0.009 5.00 0.002 50.00 -0.0015 5.00 0.000
34 70.00 2.50E-02 0.460 62.50 0.014 15.00 0.001 57.50 -0.0009 10.00 0.000
A B C D E F G H I J K L
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

35
36 Spreadsheet Documentation
37 B9=($B$5*$B$7-$B$6*A9)/($B$7+A9) F10=D10-D9
38 C9=$B$3/B9 H10=F10/G10
39 D9=$B$2-0.059*LOG10(1/C9)-$B$4 I11=(E11+E10)/2
40 C22=SQRT($B$3) J11=H11-H10
41 C23=($B$6*A23-$B$5*$B$7)/($B$7+A23) K11==E11-E10
42 E10=(A10+A9)/2 L11=J12/K12
43
44 For the titration curve, plot the potential in column D vs. the volume in column A on an XY(Scatter) plot.
45 For the first derivative, plot the derivative in column H vs. the midpoint volume in column E.
46 For the second derivative, plot the derivative in column L vs. the midpoint volume in colume I.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

21-24 For all, Ecell = Eind – ESCE

Note there are 2 mmol of Ce(IV) that react per mmol of HNO2

Pre-equivalence point region

Equivalence point

Post equivalence point region

Fundamentals of Analytical Chemistry: 8th ed. Chapter 21
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

A B C D E F G H I J K L M M O
1 21-24 Titration of HNO2 with Ce(IV) at pH 1.00
2 E0 HNO2 0.94Reaction:
3 E0 Ce(IV)/Ce(III) 1.44HNO2 + 2Ce(IV)+ H2O  NO3- + 3H+ + 2Ce(III)
4 Initial conc.HNO2 0.0500Equivalence point is at 0.0500  40.00  2/0.0800 = 50.00
5 Conc.Ce(IV) 0.0800mL of Ce(IV)
6 Vol HNO2 40.00
7 Initial soln. vol. 75.00
8 pH 1.00
9 ESCE 0.244 First Derivative Second Derivative Second
10 Vol Ce(IV), mL [NO3 ]-
[HNO2] [Ce(III)] [Ce(IV)] Eind E vs SCE Midpoint Vol. E Vol E/V Midpoint Vol. V Vol E/V2
11 5.00 0.00250 0.02250 0.823 0.58
12 10.00 0.00471 0.01882 0.833 0.59 7.50 0.010 5.00 0.002
13 15.00 0.00667 0.01556 0.840 0.60 12.50 0.007 5.00 0.001 10.00 -0.001 5.00 0.000
14 25.00 0.01000 0.01000 0.851 0.61 20.00 0.011 10.00 0.001 16.25 0.000 7.50 0.000
15 40.00 0.01391 0.00348 0.869 0.63 32.50 0.018 15.00 0.001 26.25 0.000 12.50 0.000
16 49.00 0.01581 0.00032 0.901 0.66 44.50 0.032 9.00 0.004 38.50 0.002 12.00 0.000
17 49.50 0.01590 0.00016 0.910 0.67 49.25 0.009 0.50 0.018 46.88 0.015 4.75 0.003
18 49.60 0.01592 0.00013 0.913 0.67 49.55 0.003 0.10 0.029 49.40 0.011 0.30 0.036
19 49.70 0.01594 0.00010 0.917 0.67 49.65 0.004 0.10 0.037 49.60 0.008 0.10 0.083
20 49.80 0.01596 6.41E-05 0.922 0.68 49.75 0.005 0.10 0.052 49.70 0.015 0.10 0.151
21 49.90 0.01598 3.20E-05 0.931 0.69 49.85 0.009 0.10 0.089 49.80 0.037 0.10 0.370
22 49.95 0.01599 1.60E-05 0.940 0.70 49.93 0.009 0.05 0.178 49.89 0.089 0.08 1.188
23 49.99 0.01600 3.20E-06 0.961 0.72 49.97 0.021 0.04 0.517 49.95 0.339 0.05 7.534
24 50.00 1.05 0.80 50.00 0.087 0.01 8.678 49.98 8.160 0.03 326.419
25 50.01 0.03200 6.40E-06 1.22 0.98 50.01 0.174 0.01 17.355 50.00 8.677 0.01 867.746
26 50.05 0.03199 3.20E-05 1.26 1.02 50.03 0.041 0.04 1.034 50.02 -16.321 0.03 -652.838
27 50.10 0.03197 6.39E-05 1.28 1.04 50.08 0.018 0.05 0.356 50.05 -0.678 0.05 -15.068
28 50.20 0.03195 1.28E-04 1.30 1.05 50.15 0.018 0.10 0.178 50.11 -0.178 0.08 -2.376
29 50.30 0.03192 1.92E-04 1.31 1.06 50.25 0.010 0.10 0.104 50.20 -0.074 0.10 -0.740
30 50.40 0.03190 2.55E-04 1.32 1.07 50.35 0.007 0.10 0.074 50.30 -0.030 0.10 -0.303
31 50.50 0.03187 3.19E-04 1.32 1.08 50.45 0.006 0.10 0.057 50.40 -0.017 0.10 -0.166
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

A B C D E F G H I J K L M N O
32 51.00 0.03175 6.35E-04 1.34 1.10 50.75 0.018 0.50 0.036 50.60 -0.022 0.30 -0.072
33 60.00 0.02963 0.00593 1.40 1.15 55.50 0.059 9.00 0.007 53.13 -0.029 4.75 -0.006
34 75.00 0.02667 0.01333 1.42 1.18 67.50 0.024 15.00 0.002 61.50 -0.005 12.00 0.000
35 90.00 0.02424 0.01939 1.43 1.19 82.50 0.012 15.00 0.001 75.00 -0.001 15.00 0.000
36
37
38 Spreadsheet Documentation
39 B11=($B$5*A11/2)/($B$7+A11) H12=(A12+A11)/2
40 C11=($B$4*$B$6-$B$5*A11/2)/($B$7+A11) I12=G12-G11
41 F11=$B$2-(0.0592/2)*LOG(C11/(B11*(10^-$B$8)^3)) J12=A12-A11
42 G11=F11-$B$9 K12=I12/J12
F24=((2*$B$2+$B$3)/3)-(0.0592/3)*LOG10(1/(10^-
43 $B$8)^3) L13=K13-K12 (hidden)
44 G24=F24-$B$9 M13=K13-K12 (hidden)
45 D25=($B$4*$B$6*2)/($B$7+A25) N13=H13-H12 (hidden)
46 E25=($B$5*A25-$B$4*$B$6*2)/($B$7+A25) O13=M13/N13
47 F25=$B$3-0.0592*LOG(D25/E25)
48 G25=F25-$B$9
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

The volume at which the second-derivative curve crosses zero very nearly corresponds to

the theoretical equivalence point. The slight deviation of the inflection in the curve from

the equivalence point is likely due to the non 1:1 reaction ratio of the oxidation/reduction

reaction.

21-25 The equivalence point occurs at 5.00 mL of titrant since 5 mmol of Fe2+ are consumed per

mmol of MnO4-. In order to achieve enough resolution near the equivalence point for the

derivative plots, volume increments as small as 0.001 mL are used near the equivalence

point. With modern automatic burets and syringe pumps such small volume increments

are feasible. Since the molarities of Fe2+ and permanganate are only given to 1 significant

figure, adhering to our significant figure convention would produce little resolution in the

plots. Hence, the spreadsheet uses more “significant” figures than our convention

dictates.

Pre-equivalence point region

Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

The results are shown in column F of the spreadsheet that follows.

Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

Equivalence point

The result is shown in cell F22.

Post equivalence point region

The results are shown in column F of the spreadsheet.

First- and second-derivative plots

These calculations follow the method in Applications of Microsoft Excel in Analytical

Chemistry, Chapter 7 and in Table 21-4. The titration curve is quite asymmetrical

because of the different number of electrons involved in the two half reactions. For this

case the first maximum of the first derivative does not coincide with the equivalence

point, nor does the zero crossing of the second derivative.

Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

A B C D E F G H I J K L M N
1 21-25 Titration of 25.00 mL of 0.1 M Fe(II) with 0.1 M MnO4-
2 Reaction: MnO4- + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O
3 E0 for Fe3+/Fe2+ 0.771Since 5 mmol of Fe2+ are consumed for each mmol of MnO4-,
4 E for MnO4 /Mn
0 - 2+
1.51the equivalence point will occur at 25.00 mL  0.1/(5 0.1) = 5 mL.
5 Initial conc. Fe2+ 0.1
6 Conc. MnO4- 0.1
7 Initial volume 25.00
8 [H+] 1.00 First Derivative Second Derivative
9 Vol. MnO4 , mL
-
[Fe ]
3+
[Fe ]
2+
[MnO4 ]
-
[Mn ]2+
Eind, V Midpt. Vol. E Vol E/V Midpt. Vol. V Vol. E/V2
10 1.000 0.019 0.077 0.74
11 1.500 0.028 0.066 0.75 1.250 0.01 0.500 0.028
12 2.500 0.045 0.045 0.77 2.000 0.02 1.000 0.022 1.625 -0.006 0.750 0.0
13 4.000 0.069 0.017 0.81 3.250 0.04 1.500 0.024 2.625 0.002 1.250 0.0
14 4.900 0.082 1.67E-03 0.87 4.450 0.06 0.900 0.072 3.850 0.048 1.200 0.0
15 4.950 0.083 8.35E-04 0.89 4.925 0.02 0.050 0.362 4.688 0.290 0.475 0.6
16 4.960 0.083 6.68E-04 0.89 4.955 0.01 0.010 0.579 4.940 0.217 0.030 7.2
17 4.970 0.083 5.01E-04 0.90 4.965 0.01 0.010 0.745 4.960 0.166 0.010 17
18 4.980 0.083 3.34E-04 0.91 4.975 0.01 0.010 1.048 4.970 0.303 0.010 30
19 4.990 0.083 1.67E-04 0.93 4.985 0.02 0.010 1.787 4.980 0.740 0.010 74
20 4.995 0.083 8.33E-05 0.95 4.993 0.02 0.005 3.569 4.989 1.782 0.007 238
21 4.999 0.083 1.67E-05 0.99 4.997 0.04 0.004 10.350 4.995 6.781 0.005 1507
22 5.000 1.39 5.000 0.40 0.001 396.859 4.998 386.510 0.003 154604
23 5.001 3.33E-06 0.017 1.47 5.001 0.08 0.001 79.371 5.000 -317.489 0.001 -317489
24 5.005 1.67E-05 0.017 1.47 5.003 0.01 0.004 2.069 5.002 -77.302 0.003 -30921
25 5.010 3.33E-05 0.017 1.48 5.008 0.00 0.005 0.713 5.005 -1.356 0.005 -301
26 5.020 6.66E-05 0.017 1.48 5.015 0.00 0.010 0.356 5.011 -0.356 0.007 -48
27 5.030 9.99E-05 0.017 1.48 5.025 0.00 0.010 0.208 5.020 -0.148 0.010 -15
28 5.040 1.33E-04 0.017 1.49 5.035 0.00 0.010 0.148 5.030 -0.061 0.010 -6.1
29 5.050 1.66E-04 0.017 1.49 5.045 0.00 0.010 0.115 5.040 -0.033 0.010 -3.3
30 5.100 3.32E-04 0.017 1.49 5.075 0.00 0.050 0.071 5.060 -0.043 0.030 -1.4
31 6.000 3.23E-03 0.016 1.50 5.550 0.01 0.900 0.013 5.313 -0.058 0.475 -0.1
32 7.500 7.69E-03 0.015 1.51 6.750 0.00 1.500 0.003 6.150 -0.010 1.200 0.0
33 9.000 0.012 0.015 1.51 8.250 0.00 1.500 0.002 7.500 -0.002 1.500 0.0
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

A B C D E F G H I J K L M N
34 Spreadsheet Documentation
35 B10=$B$6*A10*5/($B$7+A10) H11=F11-F10
36 C10=($B$5*$B$7-$B$6*A10*5)/($B$7+A10) I11=A11-A10
37 F10=$B$3-0.0592*LOG10(C10/B10) J11=H11/I11
38 F22=((5*$B$4+$B$3)/6)-(0.0592/6)*LOG10(1/$B$8^8) K12=(G12+G11)/2
39 D23=($B$6*A23-$B$5*$B$7/5)/($B$7+A23) L12=J12-J11
40 E23=($B$5*$B$7/5)/($B$7+A23) M12=G12-G11
41 F23=$B$4-(0.0592/5)*LOG10(E23/(D23*$B$8^8)) N12=L12/M12
42 G11=(A11+A10)/2
43 For the titration curve, Eind in column E is plotted vs. the volume of titrant in column A.
44 For the first derivative curve, the first derivative in column J is plotted vs. the midpoint volume in column G.
45 For the second derivative curve, the second derivative in column N is plotted vs. the midpoint volume in column K.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

21-26

Subtracting this latter equation from that for the initial potential gives
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

21-27

21-28 Theoretically for a cation with n = 1, the slope given by Equation 21-20 should be

+0.0592 V, or 59.2 mV. Our slope is slightly higher than this as shown in the

spreadsheet that follows, but the plot is linear. Hence, we conclude that the Nernst

equation is obeyed with a slightly larger than theoretical slope. We calculate the
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

logarithms of the unknown concentrations from

and the concentrations from

Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

A B C D E F G H
1 21-28 Lithium ion selective electrode
2
3 aLi+ log aLI+ E vs. SCE, mV
4 0.100 -1.00 1.0
5 0.050 -1.30 -30.0
6 0.010 -2.00 -60.0
7 0.001 -3.00 -138.0
8 Unk 1 -48.5
9 Unk 2 -75.3
10
11 Slope 66.6397
12 Intercept 64.8846
13 log Cunk1 -1.7015
14 Cunk1 0.020
15 log Cunk2 -2.1036
16 Cunk 2 0.008
17 Spreadsheet Documentation
18 B11=SLOPE(C4:C7,B4:B7)
19 B12=INTERCEPT(C4:C7,B4:B7)
20 B13=(C8-$B$12)/$B$11
21 B14=10^B13
22 B15=(C9-$B$12)/$B$11
23 B16=10^B15
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

21-29 Theoretically for an anion with n = 1, the slope is given by rearranging Equation 21-25.

where A represents here the F– ion. Theoretically the slope should be –0.0592 V, or –

59.2 mV. Our slope is almost exactly this as shown in the spreadsheet that follows. The

plot is linear so we can conclude that the Nernst equation is obeyed with a nearly

theoretical slope. We calculate the logarithms of the unknown concentrations from

and the concentrations from

Fundamentals of Analytical Chemistry: 8th ed. Chapter 21

A B C D E F G H
1 21-29 Fluoride ion selective electrode
2
3 cF- log cF- E vs. SCE, mV
4 5.00E-04 -3.30 0.02
5 1.00E-04 -4.00 41.4
6 5.00E-05 -4.30 61.5
7 1.00E-05 -5.00 100.2
8 Unk 1 38.9
9 Unk 2 55.3
10
11 Slope -59.2027
12 Intercept -194.9418
13 log Cunk1 -3.9498
14 Cunk1 1.12E-04
15 log Cunk2 -4.2269
16 Cunk 2 5.93E-05
17 Spreadsheet Documentation
18 B11=SLOPE(C4:C7,B4:B7)
19 B12=INTERCEPT(C4:C7,B4:B7)
20 B13=(C8-$B$12)/$B$11
21 B14=10^B13
22 B15=(C9-$B$12)/$B$11
23 B16=10^B15
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40