Introduction

In this experiment, potentiometric titration is used to determine the amount of I- and Cl-

or Br- in the solution, and the Ksp of Agl and AgBr or AgCl are also calculated. The titration in this

lab is a argentometric titration, where silver nitrate is the titrant and silver precipitate forms.1

At the end points, the number of moles of the titrant equals the number of moles of the

analyte. Also, as more AgNO3 is added, more ions are present in the solution, thus higher ionic

strength. And this would cause deviation in the calculated Ksp since concentrations, instead of

activities, are used in the calculations.

Precipitation gravimetry is a method to precipitate a compound from the solution. 2 The

reagent that is added to the solution to precipitate out the analyte is referred to as the

precipitant. 2 In order for the analyte to be precipitated, the Ksp of the compound has to be low

so that it could be insoluble in solution and be precipitated. Also, if there are other ions in the

solution, it has to be ensured that the analyte of interest has a significantly different Ksp from

them so that they would not precipitate at the same time. Nucleation is the early step of the

crystallization process. And if nucleation occurs fast, then many crystals would form at the

same time, which would then cause impurity in the analyte precipitate compound. 3 This

phenomenon is referred to as heterogenous nucleation and only occurs when there are other

substances other than the analyte and titrant in the solution. 3 And the rate of heterogenous

nucleation is much faster than that of homogenous nucleation, so the undesired compounds

could form easily. 3

Colloidal solutions are solutions with suspending particles, and the particles are evenly

spread out within the solution. 4 There are two kinds of forces that determine the stability of
colloidal solutions: the attractive forces and repulsive electric double layer forces between

particles. 5 The attractive forces include Van de Waals attraction, dipole-dipole attractions, etc.;

5
and the electric double layer is referred to the dual charge layer on the surface of a particle. A

particle in the solution would attract negative charges, which would adhere on the particle’s

surface. 6 Then, these negative charges would attract positive charges to adhere on them as

well, which leads to a formation of electric double layer.6 If the attractive forces are greater

than the repulsion force, then the particles would attract each other, causing flocculation and

unstable colloid, and vice versa. 5

Calculations – Part 1: Titration Curve

Titration of NaI and NaX with 0.1M AgNO3

300

200

100

0
-5.00 0.00 5.00 10.00 15.00 20.00 25.00
-100
E (mV)

-200

-300

-400

-500

-600
Volume AgNO3 added (mL)

Graph 1: The titration curve for the first trial titration of NaI and NaX, where X is either Br or Cl, with 0.1M AgNO3.
Note that the error bars are too small to be seen.
 Titration of NaI and NaX with 0.1M AgNO3
300

200

100

0
0.00 5.00 10.00 15.00 20.00 25.00
-100
E (mV)

-200

-300

-400

-500

-600
Volume AgNO3 added (mL)

Graph 2: The titration curve for the second trial titration of NaI and NaX, where X is either Br or Cl, with 0.1M
AgNO3. Note that the error bars are too small to be seen.

Titration of NaI and NaX with 0.1M AgNO3

300

200

100

0
0.00 5.00 10.00 15.00 20.00 25.00
E (mV)

-100

-200

-300

-400

-500
Volume AgNO3 added (mL)

Graph 3: The titration curve for the third trial titration of NaI and NaX, where X is either Br or Cl, with 0.1M AgNO3.
Note that the error bars are too small to be seen.
Calculations – Part 2: First Derivative Graph

The Derivative Graph for the First Trial Titration of NaI and NaX with 0.1M AgNO3
4000

3500

3000

2500
Δ pH/ΔV

2000

1500

1000

500

0
0.00 5.00 10.00 15.00 20.00 25.00
Average Volume Added (mL)

Graph 4: The derivative graph for the first trial titration of NaI and NaX, where X is either Br or Cl, with 0.1M
AgNO3. The two peaks occur at (8.69, 1600) and (14.69, 3550).

At the first endpoint, 8.69mL ± 0.07mL of AgNO3 was added; and at the second endpoint,

14.69mL ± 0.07mL was added.

 The Derivative Graph for the Second Trial Titration of NaI and NaX with 0.1M
AgNO3
7000

6000

5000

4000
Δ pH/ΔV

3000

2000

1000

0
0.00 5.00 10.00 15.00 20.00 25.00
Average Volume Added (mL)

Graph 5: The derivative graph for the second trial titration of NaI and NaX, where X is either Br or Cl, with 0.1M
AgNO3. The two peaks occur at (8.71, 1400) and (14.79, 6650).

8.71mL ± 0.07mL of AgNO3 was added to reach the first endpoint and 14.79mL ± 0.07mL to

reach the second.

 The Derivative Graph for the Second Trial Titration of NaI and NaX with 0.1M AgNO3
2500

2000

1500
Δ pH/ΔV

1000

500

0
0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

-500
Average Volume Added (mL)

Graph 6: The derivative graph for the second trial titration of NaI and NaX, where X is either Br or Cl, with 0.1M
AgNO3. The two peaks occur at (8.76, 1750) and (14.75, 2225).

At the first endpoint, 8.76mL ± 0.07mL AgNO3 had been added and 14.75mL ± 0.07mL of AgNO3

for the second endpoint.

Calculations – Part 3: Concentration of NaI (3rd Trial)

𝟎. 𝟏𝑴 × 𝟖. 𝟕𝟔𝒎𝑳
[𝑵𝒂𝑰] = [𝑨𝒈! ] = = 𝟎. 𝟎𝟎𝟖𝟎𝟓𝑴
(𝟏𝟎𝟎 + 𝟖. 𝟕𝟔)𝒎𝑳

"
0.0005 " 0.05 " √0.50" + 0.05"
;
𝑠 = 0.00805 × < > +< > +A C = 7.16 × 10#$ 𝑀
0.1 8.76 108.76
 𝒐𝒓𝒊𝒈𝒊𝒏𝒂𝒍 [𝑵𝒂𝑰] = 𝟎. 𝟎𝟎𝟖𝟎𝟓𝑴 × 𝟏𝟎𝟎𝒎𝑳 ÷ 𝟏𝟎𝒎𝑳 = 𝟎. 𝟎𝟖𝟎𝟓𝑴

"
7.16 × 10#$ 0.50 " 0.04 "
𝑠 = 0.0805𝑀 × ;A C +< > +< > = 0.000882𝑀
0.00805 100 10

𝟎. 𝟎𝟖𝟎𝟓𝑴 + 𝟎. 𝟎𝟖𝟎𝟏𝑴 + 𝟎. 𝟎𝟖𝟎𝟎𝑴

𝑨𝒗𝒆𝒓𝒂𝒈𝒆 [𝑵𝒂𝑰] = = 𝟎. 𝟎𝟖𝟎𝟐𝑴
𝟑

(0.0805 − 0.0802)" + (0.0801 − 0.0802)" + (0.0800 − 0.0802)"

𝑠=; = 0.000305𝑀
3−1

Calculations – Part 4: k calculation

[1𝑠𝑡 𝑡𝑟𝑖𝑎𝑙]

𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (17.57𝑚𝐿, 174𝑚𝑉)

𝟎. 𝟏𝑴 × (𝟏𝟕. 𝟓𝟕 − 𝟏𝟒. 𝟔𝟗)𝒎𝑳

[𝑨𝒈! ] = = 𝟎. 𝟎𝟎𝟐𝟒𝟓𝑴
(𝟏𝟎𝟎 + 𝟏𝟕. 𝟓𝟕)𝒎𝑳

" "
0.0005 " √0.05" + 0.05" √0.50" + 0.05"
𝑠 = 0.00245𝑀 × ;< > +A C +A C = 6.23 × 10#$ 𝑀
0.1 17.57 − 14.69 100 + 17.57

𝒌 = 𝑬 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈[𝑨𝒈! ] = 𝟎. 𝟏𝟕𝟒𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈(𝟎. 𝟎𝟎𝟐𝟒𝟓𝑴) = 𝟎. 𝟑𝟐𝟖 𝑽

6.23 × 10#$
𝑠%.%$'( )*+[-.! ] = 0.0591 × 0.434 × = 0.000652
0.00245

𝑠0 = k0.001" + 0.000652" = 0.00119𝑉

[2𝑛𝑑 𝑡𝑟𝑖𝑎𝑙]

𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (16.43𝑚𝐿, 166𝑚𝑉)

𝟎. 𝟏𝑴 × (𝟏𝟔. 𝟒𝟑 − 𝟏𝟒. 𝟕𝟗)𝒎𝑳

[𝑨𝒈! ] = = 𝟎. 𝟎𝟎𝟏𝟒𝟑𝑴
(𝟏𝟎𝟎 + 𝟏𝟔. 𝟒𝟑)𝒎𝑳
 " "
0.0005 " √0.05" + 0.05" √0.50" + 0.05"
;
𝑠 = 0.00245𝑀 × < > +A C +A C = 6.23 × 10#$ 𝑀
0.1 16.43 − 14.79 100 + 16.43

𝒌 = 𝑬 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈[𝑨𝒈! ] = 𝟎. 𝟏𝟔𝟔𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈(𝟎. 𝟎𝟎𝟏𝟒𝟑𝑴) = 𝟎. 𝟑𝟑𝟒 𝑽

6.23 × 10#$
𝑠%.%$'( )*+[-.! ] = 0.0591 × 0.434 × = 0.00112
0.00143

𝑠0 = k0.001" + 0.00112" = 0.00150𝑉

[3𝑟𝑑 𝑡𝑟𝑖𝑎𝑙]

𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (15.48𝑚𝐿, 147𝑚𝑉)

𝟎. 𝟏𝑴 × (𝟏𝟓. 𝟒𝟖 − 𝟏𝟒. 𝟕𝟓)𝒎𝑳

[𝑨𝒈! ] = = 𝟎. 𝟎𝟎𝟎𝟔𝟑𝟐𝑴
(𝟏𝟎𝟎 + 𝟏𝟓. 𝟒𝟖)𝒎𝑳

" "
0.0005 " √0.05" + 0.05" √0.50" + 0.05"
;
𝑠 = 0.00245𝑀 × < > +A C +A C = 6.14 × 10#$ 𝑀
0.1 15.48 − 14.75 100 + 15.48

𝒌 = 𝑬 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈[𝑨𝒈! ] = 𝟎. 𝟏𝟒𝟕𝑽 − 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈(𝟎. 𝟎𝟎𝟎𝟔𝟑𝟐𝑴) = 𝟎. 𝟑𝟑𝟔 𝑽

6.14 × 10#$
𝑠%.%$'( )*+[-.! ] = 0.0591 × 0.434 × = 0.00249
0.000632

𝑠0 = k0.001" + 0.00249" = 0.00268𝑉

Calculations – Part 5: Ksp of AgI

[1𝑠𝑡 𝑡𝑟𝑖𝑎𝑙]

𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (7.90𝑚𝐿, −393𝑚𝑉)

𝒎𝒐𝒍 𝑨𝒈! = 𝟎. 𝟏𝑴 × 𝟎. 𝟎𝟎𝟕𝟗𝑳 = 𝟎. 𝟎𝟎𝟎𝟕𝟗𝒎𝒐𝒍

"
0.0005 " √0.05" + 0.05"
;
𝑠 = 0.00079 × < > +A C = 8.10 × 10#1 𝑚𝑜𝑙
0.1 7.90

𝒎𝒐𝒍 𝑰! 𝒓𝒆𝒎𝒂𝒊𝒏𝒊𝒏𝒈 = 𝟎. 𝟎𝟎𝟖𝟎𝟎𝑴 × (𝟎. 𝟏 + 𝟎. 𝟎𝟎𝟕𝟗)𝑳 − 𝟎. 𝟎𝟎𝟎𝟕𝟗𝒎𝒐𝒍 = 𝟕. 𝟐𝟔𝟖 × 𝟏𝟎!𝟓 𝒎𝒐𝒍

 + +
7.10 × 10!* √0.50+ + 0.05+
𝑠#$#%& ($& )! = 0.00800 × 0.1079 × BC D +C D = 8.65 × 10!, 𝑚𝑜𝑙
0.00800 107.9

𝑠234 6" 7829:;:;. = k(8.65 × 10#1 )" + (8.10 × 10#1 )" = 1.185 × 10#$ 𝑚𝑜𝑙

[𝑰# ] = 𝟕. 𝟐𝟔𝟖 × 𝟏𝟎#𝟓 𝒎𝒐𝒍 ÷ (𝟎. 𝟏 + 𝟎. 𝟎𝟎𝟕𝟗𝟎)𝑳 = 𝟎. 𝟎𝟎𝟎𝟔𝟕𝟒𝑴

"
1.185 × 10#$ √0.50" + 0.05"
𝑠 = 0.000674𝑀 × ;A C + A C = 0.000110𝑀
7.268 × 10#$ 107.9

𝐾=>
𝑙𝑜𝑔 < > = (−0.393𝑉 − 0.328𝑉) ÷ 0.0591 = −12.2
[𝐼 # ]

𝑠 = k0.001" + 0.001" ÷ 0.0591 = 0.239

𝐾=>
= 10#("." = 6.24 × 10#(?
[𝐼 # ]

𝑠 = 6.24 × 10#(? × 2.303 × 0.239 = 3.44 × 10#(?

𝑲𝒔𝒑 = 𝟔. 𝟐𝟒 × 𝟏𝟎#𝟏𝟑 × 𝟎. 𝟎𝟎𝟎𝟔𝟕𝟒𝑴 = 𝟒. 𝟐𝟎 × 𝟏𝟎#𝟏𝟔

"
3.44 × 10#(? 0.000110 "
𝑠 = 4.20 × 10 #(1
× ;A C + < > = 2.42 × 10#(1
6.24 × 10#(? 0.000674

[2𝑛𝑑 𝑡𝑟𝑖𝑎𝑙]

𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (7.00𝑚𝐿, −420𝑚𝑉)

𝒎𝒐𝒍 𝑨𝒈! = 𝟎. 𝟏𝑴 × 𝟎. 𝟎𝟎𝟕𝟎𝟎𝑳 = 𝟎. 𝟎𝟎𝟎𝟕𝟎𝟎𝒎𝒐𝒍

"
0.0005 " √0.05" + 0.05"
;
𝑠 = 0.000700 × < > +A C = 7.89 × 10#1 𝑚𝑜𝑙
0.1 7.00

𝒎𝒐𝒍 𝑰! 𝒓𝒆𝒎𝒂𝒊𝒏𝒊𝒏𝒈 = 𝟎. 𝟎𝟎𝟖𝟎𝟏𝑴 × (𝟎. 𝟏 + 𝟎. 𝟎𝟎𝟕𝟎𝟎)𝑳 − 𝟎. 𝟎𝟎𝟎𝟕𝟎𝟎𝒎𝒐𝒍 = 𝟎. 𝟎𝟎𝟎𝟏𝟓𝟕𝟑 𝒎𝒐𝒍

+ +
7.12 × 10!* √0.50+ + 0.05+
𝑠#$#%& ($& )! = 0.00800 × 0.1079 × BC D +C D = 8.61 × 10!, 𝑚𝑜𝑙
0.00801 107

𝑠234 6" 7829:;:;. = k(8.61 × 10#1 )" + (7.89 × 10#1 )" = 1.168 × 10#$ 𝑚𝑜𝑙
 [𝑰# ] = 𝟎. 𝟎𝟎𝟎𝟏𝟓𝟕𝟑𝒎𝒐𝒍 ÷ (𝟎. 𝟏 + 𝟎. 𝟎𝟎𝟕)𝑳 = 𝟎. 𝟎𝟎𝟏𝟒𝟕𝑴

"
1.168 × 10#$ √0.50" + 0.05"
𝑠 = 0.00147𝑀 × ;A C +A C = 0.000109𝑀
0.0001573 107

𝐾=>
𝑙𝑜𝑔 < > = (−0.420𝑉 − 0.334𝑉) ÷ 0.0591 = −12.8
[𝐼 # ]

𝑠 = k0.001" + 0.001" ÷ 0.0591 = 0.239

𝐾=>
= 10#(".E = 1.74 × 10#(?
[𝐼 # ]

𝑠 = 1.74 × 10#(? × 2.303 × 0.239 = 9.57 × 10#(F

𝑲𝒔𝒑 = 𝟏. 𝟕𝟒 × 𝟏𝟎#𝟏𝟑 × 𝟎. 𝟎𝟎𝟏𝟒𝟕𝑴 = 𝟐. 𝟓𝟓 × 𝟏𝟎#𝟏𝟔

"
9.57 × 10#(F 0.000109 "
𝑠 = 2.55 × 10 #(1
× ;A C + < > = 1.42 × 10#(1
1.74 × 10#(? 0.00147

[3𝑟𝑑 𝑡𝑟𝑖𝑎𝑙]

𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (7.97𝑚𝐿, −388𝑚𝑉)

𝒎𝒐𝒍 𝑨𝒈! = 𝟎. 𝟏𝑴 × 𝟎. 𝟎𝟎𝟕𝟗𝟕𝑳 = 𝟎. 𝟎𝟎𝟎𝟕𝟗𝟕𝒎𝒐𝒍

"
0.0005 " √0.05" + 0.05"
;
𝑠 = 0.000797 × < > +A C = 8.12 × 10#1 𝑚𝑜𝑙
0.1 7.97

𝒎𝒐𝒍 𝑰! 𝒓𝒆𝒎𝒂𝒊𝒏𝒊𝒏𝒈 = 𝟎. 𝟎𝟎𝟖𝟎𝟓𝑴 × (𝟎. 𝟏 + 𝟎. 𝟎𝟎𝟕𝟗𝟕)𝑳 − 𝟎. 𝟎𝟎𝟎𝟕𝟗𝟕𝒎𝒐𝒍 = 𝟕. 𝟐𝟔𝟒 × 𝟏𝟎!𝟓 𝒎𝒐𝒍

+ +
7.16 × 10!* √0.50+ + 0.05+
𝑠#$#%& ($& )! = 0.00805 × 0.10797 × BC D +C D = 8.66 × 10!, 𝑚𝑜𝑙
0.00805 107.97

𝑠234 6" 7829:;:;. = k(8.66 × 10#1 )" + (8.12 × 10#1 )" = 1.187 × 10#$ 𝑚𝑜𝑙

[𝑰# ] = 𝟕. 𝟐𝟔𝟒 × 𝟏𝟎#𝟓 𝒎𝒐𝒍 ÷ (𝟎. 𝟏 + 𝟎. 𝟎𝟎𝟕𝟗𝟕)𝑳 = 𝟎. 𝟎𝟎𝟎𝟔𝟕𝟑𝑴

"
1.187 × 10#$ √0.50" + 0.05"
𝑠 = 0.000672𝑀 × ;A C + A C = 0.000110𝑀
7.264 × 10#$ 107.97
 𝐾=>
𝑙𝑜𝑔 < > = (−0.388𝑉 − 0.336𝑉) ÷ 0.0591 = −12.3
[𝐼 # ]

𝑠 = k0.001" + 0.001" ÷ 0.0591 = 0.239

𝐾=>
= 10#(".? = 5.60 × 10#(?
[𝐼 # ]

𝑠 = 5.60 × 10#(? × 2.303 × 0.239 = 3.09 × 10#(?

𝑲𝒔𝒑 = 𝟓. 𝟔𝟎 × 𝟏𝟎#𝟏𝟑 × 𝟎. 𝟎𝟎𝟎𝟔𝟕𝟑𝑴 = 𝟑. 𝟕𝟕 × 𝟏𝟎#𝟏𝟔

"
3.09 × 10#(? 0.000110 "
𝑠 = 3.77 × 10 #(1
× ;A C +< > = 2.17 × 10#(1
5.60 × 10#(? 0.000673

𝟒. 𝟐𝟎 × 𝟏𝟎#𝟏𝟔 + 𝟐. 𝟓𝟓 × 𝟏𝟎#𝟏𝟔 + 𝟐. 𝟏𝟕 × 𝟏𝟎#𝟏𝟔

𝑨𝒗𝒆𝒓𝒂𝒈𝒆 𝑲𝒔𝒑 = = 𝟑. 𝟓𝟏 × 𝟏𝟎#𝟏𝟔
𝟑

(4.20 × 10!-, − 3.51 × 10!-, )+ + (2.55 × 10!-, − 3.51 × 10!-, )+ + (2.17 × 10!-, − 3.51 × 10!-, )+
𝑠=B
3−1

= 8.56 × 10!-.

Calculations – Part 6: Concentration of NaX (3rd Trial)

𝟎. 𝟏𝑴 × (𝟏𝟒. 𝟕𝟓 − 𝟖. 𝟕𝟔)𝒎𝑳
[𝑵𝒂𝑿] = [𝑨𝒈! ] = = 𝟎. 𝟎𝟎𝟓𝟐𝟐𝑴
(𝟏𝟎𝟎 + 𝟏𝟒. 𝟕𝟓)𝒎𝑳

" "
0.0005 " √0.05" + 0.05" √0.50" + 0.05"
𝑠 = 0.00522 × ;< > +A C +A C = 7.07 × 10#$ 𝑀
0.1 14.75 − 8.76 100 + 14.75

𝒐𝒓𝒊𝒈𝒊𝒏𝒂𝒍 [𝑵𝒂𝑿] = 𝟕. 𝟎𝟕 × 𝟏𝟎#𝟓 𝑴 × 𝟏𝟎𝟎𝒎𝑳 ÷ 𝟏𝟎𝒎𝑳 = 𝟎. 𝟎𝟓𝟐𝟐𝑴

"
7.07 × 10#$ 0.50 " 0.04 "
𝑠 = 0.0805𝑀 × ;A C +< > +< > = 0.000782𝑀
0.00522 100 10

𝟎. 𝟎𝟓𝟐𝟐𝑴 + 𝟎. 𝟎𝟓𝟑𝟎𝑴 + 𝟎. 𝟎𝟓𝟐𝟑𝑴

𝑨𝒗𝒆𝒓𝒂𝒈𝒆 [𝑵𝒂𝑿] = = 𝟎. 𝟎𝟓𝟐𝟓𝑴
𝟑
 (0.0522 − 0.0525)" + (0.0530 − 0.0525)" + (0.0523 − 0.0525)"
𝑠=; = 0.000415𝑀
3−1

Calculations – Part 7: Ksp of AgX

[1𝑠𝑡 𝑡𝑟𝑖𝑎𝑙]

𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (14.37𝑚𝐿, −218𝑚𝑉)

𝒎𝒐𝒍 𝑨𝒈! = 𝟎. 𝟏𝑴 × (𝟎. 𝟎𝟏𝟒𝟑𝟕 − 𝟎. 𝟎𝟎𝟖𝟔𝟗)𝑳 = 𝟎. 𝟎𝟎𝟎𝟓𝟕𝟎𝒎𝒐𝒍

"
0.0005 " √0.05" + 0.05"
;
𝑠 = 0.000570 × < > +A C = 7.64 × 10#1 𝑚𝑜𝑙
0.1 14.37 − 8.69

𝒎𝒐𝒍 𝑿! 𝒓𝒆𝒎𝒂𝒊𝒏𝒊𝒏𝒈 = 𝟎. 𝟎𝟎𝟓𝟐𝟑𝑴 × (𝟎. 𝟏 + 𝟎. 𝟎𝟏𝟒𝟑𝟕)𝑳 − 𝟎. 𝟎𝟎𝟎𝟓𝟕𝟎𝒎𝒐𝒍 = 𝟐. 𝟖𝟗 × 𝟏𝟎!𝟓 𝒎𝒐𝒍

+ +
6.76 × 10!* √0.50+ + 0.05+
𝑠#$#%& ($& / ! = 0.00523 × 0.11437 × BC D +C D = 8.17 × 10!, 𝑚𝑜𝑙
0.00523 114.37

𝑠234 G " 7829:;:;. = k(8.17 × 10#1 )" + (7.64 × 10#1 )" = 1.119 × 10#$ 𝑚𝑜𝑙

[𝑿# ] = 𝟐. 𝟖𝟗 × 𝟏𝟎#𝟓 𝒎𝒐𝒍 ÷ (𝟎. 𝟏 + 𝟎. 𝟎𝟏𝟒𝟑𝟕)𝑳 = 𝟎. 𝟎𝟎𝟎𝟐𝟓𝟑𝑴

"
1.119 × 10#$ √0.50" + 0.05"
;
𝑠 = 0.000253𝑀 × A C +A C = 9.78 × 10#$ 𝑀
2.89 × 10#$ 114.37

𝐾=>
𝑙𝑜𝑔 < > = (−0.218 − 0.328𝑉) ÷ 0.0591 = −9.24
[𝑋 # ]

𝑠 = k0.001" + 0.001" ÷ 0.0591 = 0.239

𝐾=>
= 10#'."F = 5.71 × 10#(%
[𝑋 # ]

𝑠 = 5.71 × 10#(% × 2.303 × 0.239 = 3.14 × 10#(%

𝑲𝒔𝒑 = 𝟓. 𝟕𝟏 × 𝟏𝟎#𝟏𝟎 × 𝟎. 𝟎𝟎𝟎𝟐𝟓𝟑𝑴 = 𝟏. 𝟒𝟒 × 𝟏𝟎#𝟏𝟑

 " "
3.14 × 10#(% 9.78 × 10#$
𝑠 = 1.44 × 10 #(?
× ;A C +A C = 9.71 × 10#(F
5.71 × 10#(% 0.000253

[2𝑛𝑑 𝑡𝑟𝑖𝑎𝑙]

𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (14.50𝑚𝐿, −201𝑚𝑉)

𝒎𝒐𝒍 𝑨𝒈! = 𝟎. 𝟏𝑴 × (𝟎. 𝟎𝟏𝟒𝟓𝟎 − 𝟎. 𝟎𝟎𝟖𝟕𝟏)𝑳 = 𝟎. 𝟎𝟎𝟎𝟓𝟖𝟎𝒎𝒐𝒍

"
0.0005 " √0.05" + 0.05"
𝑠 = 0.000580 × ;< > +A C = 7.64 × 10#1 𝑚𝑜𝑙
0.1 14.50 − 8.71

𝒎𝒐𝒍 𝑿! 𝒓𝒆𝒎𝒂𝒊𝒏𝒊𝒏𝒈 = 𝟎. 𝟎𝟎𝟓𝟑𝟎𝑴 × (𝟎. 𝟏 + 𝟎. 𝟎𝟏𝟒𝟓𝟎)𝑳 − 𝟎. 𝟎𝟎𝟎𝟓𝟖𝟎𝒎𝒐𝒍 = 𝟐. 𝟕𝟎 × 𝟏𝟎!𝟓 𝒎𝒐𝒍

+ +
7.28 × 10!* √0.50+ + 0.05+
𝑠#$#%& ($& / ! = 0.00530 × 0.11450 × BC D +C D = 8.75 × 10!, 𝑚𝑜𝑙
0.00530 114.50

𝑠234 G " 7829:;:;. = k(8.75 × 10#1 )" + (7.64 × 10#1 )" = 1.16 × 10#$ 𝑚𝑜𝑙

[𝑿# ] = 𝟐. 𝟕𝟎 × 𝟏𝟎#𝟓 𝒎𝒐𝒍 ÷ (𝟎. 𝟏 + 𝟎. 𝟎𝟏𝟒𝟓𝟎)𝑳 = 𝟎. 𝟎𝟎𝟎𝟐𝟑𝟓𝑴

"
1.16 × 10#$ √0.50" + 0.05"
𝑠 = 0.000235𝑀 × ;A C + A C = 0.000101𝑀
2.70 × 10#$ 114.50

𝐾=>
𝑙𝑜𝑔 < > = (−0.201 − 0.334𝑉) ÷ 0.0591 = −9.05
[𝑋 # ]

𝑠 = k0.001" + 0.001" ÷ 0.0591 = 0.239

𝐾=>
= 10#'.%$ = 8.81 × 10#(%
[𝑋 # ]

𝑠 = 8.81 × 10#(% × 2.303 × 0.239 = 4.86 × 10#(%

𝑲𝒔𝒑 = 𝟖. 𝟖𝟏 × 𝟏𝟎#𝟏𝟎 × 𝟎. 𝟎𝟎𝟎𝟐𝟑𝟓𝑴 = 𝟐. 𝟎𝟖 × 𝟏𝟎#𝟏𝟑

"
4.86 × 10#(% 0.000101 "
𝑠 = 2.08 × 10 #(?
× ;A C + < > = 1.45 × 10#(?
8.81 × 10#(% 0.000235

[3𝑟𝑑 𝑡𝑟𝑖𝑎𝑙]
 𝑝𝑜𝑖𝑛𝑡 𝑝𝑖𝑐𝑘𝑒𝑑: (12.47𝑚𝐿, −240𝑚𝑉)

𝒎𝒐𝒍 𝑨𝒈! = 𝟎. 𝟏𝑴 × (𝟎. 𝟎𝟏𝟐𝟒𝟕 − 𝟎. 𝟎𝟎𝟖𝟕𝟔)𝑳 = 𝟎. 𝟎𝟎𝟎𝟑𝟕𝟏𝒎𝒐𝒍

"
0.0005 " √0.05" + 0.05"
;
𝑠 = 0.000371 × < > +A C = 7.31 × 10#1 𝑚𝑜𝑙
0.1 12.47 − 8.76

𝒎𝒐𝒍 𝑿! 𝒓𝒆𝒎𝒂𝒊𝒏𝒊𝒏𝒈 = 𝟎. 𝟎𝟎𝟓𝟐𝟐𝑴 × (𝟎. 𝟏 + 𝟎. 𝟎𝟏𝟐𝟒𝟕)𝑳 − 𝟎. 𝟎𝟎𝟎𝟑𝟕𝟏𝒎𝒐𝒍 = 𝟎. 𝟎𝟎𝟎𝟐𝟏𝟔 𝒎𝒐𝒍

+ +
7.31 × 10!, √0.50+ + 0.05+
𝑠#$#%& ($& / ! = 0.00522 × 0.11247 × BC D +C D = 8.37 × 10!, 𝑚𝑜𝑙
0.000371 112.47

𝑠234 G " 7829:;:;. = k(8.37 × 10#1 )" + (7.31 × 10#1 )" = 1.112 × 10#$ 𝑚𝑜𝑙

[𝑿# ] = 𝟎. 𝟎𝟎𝟎𝟐𝟏𝟔𝒎𝒐𝒍 ÷ (𝟎. 𝟏 + 𝟎. 𝟎𝟏𝟐𝟒𝟕)𝑳 = 𝟎. 𝟎𝟎𝟏𝟗𝟐𝑴

"
1.112 × 10#$ √0.50" + 0.05"
𝑠 = 0.00192𝑀 × ;A C +A C = 9.92 × 10#$ 𝑀
0.000216 112.47

𝐾=>
𝑙𝑜𝑔 < > = (−0.240𝑉 − 0.336𝑉) ÷ 0.0591 = −9.75
[𝑋 # ]

𝑠 = k0.001" + 0.001" ÷ 0.0591 = 0.239

𝐾=>
= 10#'.I$ = 1.79 × 10#(%
[𝑋 # ]

𝑠 = 1.79 × 10#(? × 2.303 × 0.239 = 9.86 × 10#((

𝑲𝒔𝒑 = 𝟏. 𝟕𝟗 × 𝟏𝟎#𝟏𝟎 × 𝟎. 𝟎𝟎𝟏𝟗𝟐𝑴 = 𝟑. 𝟒𝟒 × 𝟏𝟎#𝟏𝟑

" "
9.86 × 10#(( 9.92 × 10#$
𝑠 = 3.44 × 10 #(?
× ;A C + A C = 1.90 × 10#(?
1.79 × 10#(% 0.00192

𝟏. 𝟒𝟒 × 𝟏𝟎#𝟏𝟑 + 𝟐. 𝟎𝟖 × 𝟏𝟎#𝟏𝟑 + 𝟑. 𝟒𝟒 × 𝟏𝟎#𝟏𝟕

𝑨𝒗𝒆𝒓𝒂𝒈𝒆 𝑲𝒔𝒑 = = 𝟐. 𝟑𝟏𝟖 × 𝟏𝟎#𝟏𝟑
𝟑

(1.44 × 10!-0 − 2.318 × 10!-0 )+ + (2.08 × 10!-0 − 2.318 × 10!-0 )+ + (3.44 × 10!-. − 2.318 × 10!-0 )+
𝑠=B
3−1
 = 1.02 × 10!-0

𝑁𝑎𝑋 𝑖𝑠 𝑁𝑎𝐵𝑟 𝑠𝑖𝑛𝑐𝑒 𝑡ℎ𝑒 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑣𝑎𝑙𝑢𝑒 𝑓𝑜𝑟 𝐾=> 𝑜𝑓 𝐴𝑔𝐵𝑟 𝑖𝑠 5.35 × 10#(? .

Discussion

Potentiometric titrations help determine the concentration of an analyte by measuring

the potentials of the solution.7 And this type of titrations require an indicator electrode and a

reference electrode. The indicator electrode will respond to the change as the analyte activity

changes, whereas the reference electrode would remain fixed and have a stable response.8 And

the reason why there has to be two electrodes is because potential is a relative measurement,

so the potential has to be measured relative to a standard, which is the reference electrode.

The reference electrode would be assigned to be the anode, and the indicator electrode the

cathode.9 However, since in the experiment, Ag+ is being reduced, its potential is multiplied by -

1.

As the titrant is added into a solution with an unknown amount of analyte, the potential

of the solution changes. In this experiment, Ag+ is added into the solution containing l- and Br-

or CI-. Since the Ksp value of AgI is much lower than that of AgBr or AgCl, AgI would precipitate

first. The precipitation reaction of AgI is 𝐴𝑔! + 𝐼 # ⇌ 𝐴𝑔𝐼. Initially, as Ag+ is added, the

equilibrium would shift to the right, according to Le Chatelier’s Principle, and a new equilibrium

would be established. Eventually, as the I- in the solution is used up by the Ag+ added, all I-

would be precipitated out. This is referred to as the equivalence point, where mol of Ag+ equals

mol of I-. Therefore, the initial concentration of I- could be determined. Also, since all the I- is

used up in the solution, the concentration of Ag+ increases sharply, which causes the potential

to also rise abruptly. After that, another flat region will occur as the equilibrium of the next
precipitation reaction between Ag+ and Br- or Cl- is established. Then, at the second equivalence

point, the mol of Br- or Cl- equals the mol of Ag+, and the concentration of the halide ion could

also be determined. After the second equivalence point, all the halides are precipitated.

Therefore, the only ions present in the solution is Ag+. Therefore, as Ag+ is added to the

solution, there are more Ag+ in the solution, so the potential of the solution steadily increases.

Ksp is the equilibrium constant of a precipitation reaction. The higher the Ksp value, the

more soluble the substance is. In this experiment, one of the precipitation reactions is 𝐴𝑔! +

𝐼 # ⇌ 𝐴𝑔𝐼. And the solubility constant is calculated as 𝐾=> = [𝐴𝑔! ][𝐼 # ]. At equilibrium, the rate

of the forward reaction is the same as that of the reverse reaction. And when stress is added to

one side, the reaction tends to shift to the other side to reduce the stress. However, in high

ionic strength solutions, the Ksp is not calculated using the concentrations but using the

activities. And as the ionic strength of a solution increases, the solubility of the salt increases

because the salt ions are shielded by the other ions in solution.
Results Sheet

Volume AgNO3 added (mL)

Trial First End Point Second End Point

1 8.69 ± 0.07 mL 14.69 ± 0.07 mL

2 8.71 ± 0.07 mL 14.79 ± 0.07 mL

3 8.76 ± 0.07 mL 14.75 ± 0.07 mL

Average 8.72 ± 0.04 mL 14.74 ± 0.05 mL

[𝐴𝑔𝑁𝑂? ] = 0.1000 ± 0.0005𝑀

[𝑁𝑎𝐼] 𝑖𝑛 𝑡ℎ𝑒 𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒: 0.0802 ± 0.0003𝑀

[𝑁𝑎𝐵𝑟] 𝑖𝑛 𝑡ℎ𝑒 𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑠𝑎𝑚𝑝𝑙𝑒: 0.0525 ± 0.0004𝑀

𝐾=> 𝑜𝑓 𝐴𝑔𝐼: 3.51 × 10#(1 ± 8.56 × 10#(I

𝐾=> 𝑜𝑓 𝐴𝑔𝐵𝑟: 2.08 × 10#(? ± 1.45 × 10#(?

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