Because the undissociatedacid is a neutral species, It is a good approximation to

set its activity equal to its concentration. The activity of the lonic species produced
upon dissociation are given by 𝑎𝐻 ∗ = 𝑦∓ 𝑎𝐻 ∗ and 𝑎λ = 𝑦± 𝑐λ . the equilibrium
expression becomes.
𝑦± 𝑐𝐻 ∗ 𝑦 1𝑐𝑘 (𝑌± )2 𝑚
𝑚
°
𝐾𝑎 = = 𝑚
𝑐𝐻𝐴 𝐶0 − °
𝑚

This expression has two unknowns. We solve for m using an iterative method. We
first assume that 𝑦1 = 1 and solve for m. we use this value of m to calculate 𝑦± and
using this value, recalculate m. we repeat this procedure until 𝑥 is sufficiently
constant.
𝑚 2
( )
𝑚° −2
𝑚 = 2.50 × 10
0.093 − °
𝑚
The ionic strength and 𝑦± are given by
𝑚
𝐼 = 𝑚° = 𝑚 = 0.0373 𝑚𝑜𝑙 𝑘𝑔−1

Ln 𝑦± = −1.173 × 1 × √0.0373 = −0.2266

𝑦± = 0.797

We use this value of 𝑦± to calculate a new value of m.

𝑚 2
( ) × (0.787)2
𝑚° = 2.50 × 10−2
𝑚
0.093 − °
𝑚
𝑚 = 4.39 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

The ionic strength and 𝑦± are given by

𝑚
𝐼= (2) = 𝑚 = 0.0439 𝑚𝑜𝑙 𝑘𝑔−1
2

ln𝑦± =-1.173×1×√0.0439 = -0.2459

𝑦± = 0.782

We recalculate m and 𝑦± and iterate several times.

 𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 2.50 × 10−2 with 𝑦± = 0.782
0.093− °
𝑚

𝑚 = 4.45 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

𝑚
𝐼= (2) = 𝑚 = 4.45 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1
2

𝑙𝑛𝑦±=−1.173×1×√4.45×10−2 =−0.2475
𝑦± =0.781

When 𝑦± = 0.781,
𝑚 2 2
( ) 𝑦 ±
𝑚° −2
𝑚 = 2.50 × 10
0.093 − °
𝑚
𝑚 = 4.45 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

This is a sufficiently good result, and we calculate the degree of dissociation to be

0,0446 𝑚𝑜𝑙 𝑘𝑔−1
× 100% = 48%
0,093 𝑚𝑜𝑙 𝑘𝑔−1

(b) we first calculate the degree of dissociation using the limiting law and
neglecting the increase in ionic strength produced by the acid dissociation.
𝑚
𝐼= (2) = 𝑚 = 0.200 𝑚𝑜𝑙 𝑘𝑔−1
2

ln𝑦± =-1.173×1×√0.200 = -0.5426

𝑦± = 0.592
𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 2.50 × 10−2 whit 𝑦± =0.592
0.093− °
𝑚

𝑚 = 5.33 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

We nwxt calculate the total concentration of the ions in the solution when 𝑦± =
0.592
𝑚
𝐼 = 0.200 𝑚𝑜𝑙 𝑘𝑔−1 + (2) = 0.253 𝑚𝑜𝑙 𝑘𝑔−1
2

ln𝑦± =-1.173×1×√0.253 = -0.5903

𝑦± = 0.554

We next calculate the total concentration of the ions the solution when 𝑦± = 0.554.
 𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 2.50 × 10−2
0.093− °
𝑚

𝑚 = 5.54 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

We calculate m and 𝑦± and iterate.

𝑚 𝑚𝑜𝑙 𝑚𝑜𝑙
𝐼= (2) + 0.200 = 𝑚 + 0.200 = 0.2554 𝑚𝑜𝑙/𝑘𝑔−1
2 𝑘𝑔 𝑘𝑔

ln𝑦± =-1.173×1×√0.2554 = -0.5928

𝑦± = 0.553
𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 2.50 × 10−2
0.093− °
𝑚

whit 𝑦± =0.553

𝑚 = 5.54 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

This is sufficiently good result, and we calculate the degree of dissociation to be

0.0554
=60.%
0.093

(c) we use the value of 𝑦±=0.718 from table 10.3.

𝑚 2
( °) 𝑦2±
𝑚
𝑚 = 2.50 × 10−2
0.093− °
𝑚

𝑚 = 4.71 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

0.0471
The degree of dissociation is = 51%.
0.093

P10.6 Calculate the mean ionic activity of a 0.0350 m 𝑁𝑎3 𝑃𝑂4 solution for which
the mean activity coefficient is .0.685
1⁄
(𝑣+𝑣 + 𝑣−𝑣 −) 𝑣 𝑚 1⁄
𝑎± = ( ) 𝑦± = (33 11 ) 4 0.350 × 0.685 = 0.0547
𝑚°

P10.7 At 25° 𝐶, the equilibrium constant for the dissociation of acetic acid, 𝑘𝑎 , is
1.75×10−5. Using the Debye-Huckel limiting law, calculate the degree of
dissociation in 0.150 m and 1.50 m solutions using an iterative calculation until the
answer is constant in the second decimal place. Compare these values with what
you would obtain if the ionic interactions had been ignored. Compare your results
with the degree of dissociation of the acid assuming 𝑦± = 1.

A weak acid dissociates according to the following equilibrium reaction.

𝐻𝐴(𝑎𝑞) ⇌ 𝐻 + (𝑎𝑞) + 𝐴− (𝑎𝑞)

𝑎𝐻+𝑎λ
𝐾𝑎 = 𝑎𝐻𝐴

Because the dissociated acid is a neutral species, it is a good approximation to set

activity equal to its concentration. The activity of the ionic species produced upon
dissociation are given by 𝑎𝐻 += 𝑦±𝑐 + and 𝑦±𝑐𝜆 . The equilibrium expression
𝐻
becomes
𝑚
𝑦± 𝑐𝐻+ 𝑦± 𝑐𝜆 (𝑦± )2 °
𝑚
𝐾𝑎 = = 𝑚
𝐶𝐻𝐴 𝐶 °− °
𝑚

This expression has two unknowns we solve for m using an iterative method. We
first assume that 𝑦± = 1 and solve for m. We use this value of m to calculate 𝑦±
and using this value, recalculate m. we repeat this procedure until x is sufficiently
constant.

𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) ⇌ 𝐶𝐻3 𝐶𝑂𝑂− (𝑎𝑞) + 𝐻 + (𝑎𝑞)

For 0.150m

𝑚2 𝑦±2
= 1.75 × 10−5
150 𝑚𝑜𝑙 𝑘𝑔−1 − 𝑚

When 𝑦± = 1

𝑚 = 1.611 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

𝑚
𝐼= (2) = 𝑚 = 1.611 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1
2

ln𝑦± =-1.173×1×√1.689 × 10−3 = -0.048020

𝑦± = 0.953

When 𝑦± = 0.953
𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 1.75 × 10−5
0.150− °
𝑚
 𝑚 = 1.691 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

This result has converged sufficiently to calculate the degree of dissociations.

𝑚 = 1.691 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

1.691×10−3 𝑚𝑜𝑙 𝑘𝑔−1
𝑚= × 100% = 1.13%
0.150 𝑚𝑜𝑙 𝑘𝑔−1

For 1.50 m

𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 1.75 × 10−5
1.50− °
𝑚

When 𝑦± = 1

𝑚 = 5.115 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

𝐼 = 𝑚 = 5.115 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

Ln𝑦± = −0.8389

𝑦± = 0.920

When 𝑦± = 0.920
𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 1.75 × 10−5
1.50− °
𝑚

𝑚 = 5.561 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

We iterate several times.

When m=5.561 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

𝑚
𝐼= (2) = 𝑚 = 5.561 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1
2

ln𝑦± =-1.173×1×√5.561 × 10−3 = -0.08748

When 𝑦± = 0.916
 𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 1.75 × 10−5
1.50− °
𝑚

𝑚 = 5.581 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1 → 5.58 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

This result has converged sufficiently to calculate the degreed of dissociation.

𝑚 = 5.581 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

5.581×10−3 𝑚𝑜𝑙 𝑘𝑔−1
× 100% = 0.372%
1.50 𝑚𝑜𝑙 𝑘𝑔−1

If ionic interactions are ignored.

For 0.150 m
𝑚 2
( °) 𝑦2±
𝑚
𝑚 = 1.75 × 10−5
1.50− °
𝑚

𝑚 = 1.61 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

1.61×10−3
× 100% = 1.07%
0.150

For 0.150 m
𝑚 2
( °) 𝑦2±
𝑚
𝑚 = 1.75 × 10−5
1.50− °
𝑚

𝑚 = 5.11 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

5.11×10−3
× 100% = 0.341%
1.50

P10.8 From the data I table 10.3 (see appendix B, Data Tables), calculate the
activity in 0.200 m

Solutions assuming complete dissociation off

a. KCL b. 𝑁𝐴2 𝑆𝑂4 c. Mg𝐶𝑙2

(a) KCL 0.200 𝑦± = 0.718

𝑚 𝑣
𝑎± = ( 𝑚±° ) 𝑦± ; 𝑚± = 𝑚+𝑣 = 𝑚−𝑣

2
𝑚± = (0.200)(0.200); 𝑚± = 0.200 𝑚𝑜𝑙 𝑘𝑔−1
 𝑎± = (0.200)(0.718) = 0.144

(b) 𝑁𝐴2 𝑆𝑂4 0.200m 𝑦± = 0.209

3
𝑚± = (2 × 0.200)2 (0.200)1

𝑚± = 0.317𝑚𝑜𝑙 𝑘𝑔−1

𝑎± = (0.317)(0.209) = 0.0663

(c) Mg𝐶𝑙2 0.200m 𝑦± = 0.489

3
𝑚± = (0.200)(2 × 0.200)2

𝑚± = 0.317𝑚𝑜𝑙 𝑘𝑔−1

𝑎± = (0.317)(0.489) = 0.155

P10.9 Estimate the degree of dissociation of a 0.200 m solution of nitrous

acido(𝐾𝑎 = 4.00 × 10−4 ) 𝑡ℎ𝑎𝑡 𝑖𝑠 𝑎𝑙𝑠𝑜 0.500 m in the strong electrolyte given in parts
(a)-(c). use the data tables to obtain 𝑦± as the electrolyte concentration is too hight
to use the debye-Huckel limiting law.

a. Ba𝐶𝐿 2 b. 𝐾𝑂𝐻 c. Ag𝑁𝑂3

Compare your results whith the degree of dissociation of the acid assuming 𝑦± =
1.

In each case, the activity of the ions produced in the dissociation of acetic acid is
determined by the strong electrolyte.

(a) Ba𝐶𝐿 2
From table 10.3, 𝑦± =0,397

𝑚 𝑚 2
2 2( )
𝑦± ( ° )2 (0.397) 𝑚°
−4 𝑚
4.00 × 10 = 𝑚 = 𝑚
0.200− ° 0.200− °
𝑚 𝑚

𝑚 = 0,0213𝑚𝑜𝑙 𝑘𝑔−1
0,0213𝑚𝑜𝑙 𝑘𝑔−1
× 100% = 10,6%
0,200𝑚𝑜𝑙 𝑘𝑔−1

(b) KOH
From table 10.3, 𝑦± = 0.732
 𝑚 2
2( )
−4 (0.732) 𝑚°
4.00 × 10 = 𝑚
0.200− °
𝑚

𝑚 = 1.19 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

1.19×10−2 𝑚𝑜𝑙 𝑘𝑔−1
× 100% = 5.92%
0,200𝑚𝑜𝑙 𝑘𝑔−1

(c ) Ag𝑁𝑂3

From table 10.3, 𝑦± = 1,

𝑚 𝑚 2
2 2( )
𝑦± ( ° )2 (0.536) 𝑚°
1.75 × 10−5 = 𝑚
𝑚 = 𝑚
0.200− ° 0.200− °
𝑚 𝑚

𝑚 = 1.60 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

1.60×10−2 𝑚𝑜𝑙 𝑘𝑔−1
× 100% = 8.00%
0.200 𝑚𝑜𝑙 𝑘𝑔−1

Assuming 𝑦± = 1
2 𝑚 𝑚
𝑦± ( ° )2 ( ° )2
−4 𝑚 𝑚
4.00 × 10 = 𝑚 = 𝑚
0.200− ° 0.200− °
𝑚 𝑚

𝑚 = 8.75 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

8.75×10−3 𝑚𝑜𝑙 𝑘𝑔−1
× 100% = 4.37%
0.200 𝑚𝑜𝑙 𝑘𝑔−1

P10.10 calculate ∆𝐻𝑅° and ∆𝐺𝑅° for the reaction Ba(𝑁𝑂3 )(𝑎𝑞) + 2𝐾𝐶𝐿(𝑎𝑞) →
𝐵𝑎𝐶𝑙2 (𝑠) + 2𝐾𝑁𝑂3 (𝑎𝑞)

∆𝐺𝑅° = ∆𝐺𝑓° (𝐵𝑎𝐶𝑙2 , 𝑠) + 2∆𝐺𝑓° (𝐾 + , 𝑎𝑞) + 2∆𝐺𝑓° (𝑁𝑂3− , 𝑎𝑞) − ∆𝐺𝑓° (𝐵𝑎2+ , 𝑎𝑞) −
2∆𝐺𝑓° (𝑁𝑂3− , 𝑎𝑞) − 2∆𝐺𝑓° (𝑁𝑂3− , 𝑎𝑞) − 2∆𝐺𝑓° (𝐾 + , 𝑎𝑞) − 2∆𝐺𝑓° (𝐶𝑙 − 𝑎𝑞)

∆𝐺𝑅° = ∆𝐺𝑓° (𝐵𝑎𝐶𝑙2 , 𝑠) − ∆𝐺𝑓° (𝐵𝑎2+ , 𝑎𝑞) − 2∆𝐺𝑓° (𝐶𝑙 − 𝑎𝑞)

∆𝐺𝑅° =-806.7 𝐾𝐽 𝑚𝑜𝑙 −1 +560.8 𝐾𝐽 𝑚𝑜𝑙 −1 +2 × 131.2 𝐾𝐽 𝑚𝑜𝑙 −1 =

16.5 𝐾𝐽 𝑚𝑜𝑙 −1

∆𝐻𝑅° = ∆𝐺𝑓° (𝐵𝑎𝐶𝑙2 , 𝑠) − ∆𝐺𝑓° (𝐵𝑎2+ , 𝑎𝑞) − 2∆𝐻𝑓° (𝐶𝑙 − 𝑎𝑞)

 ∆𝐻𝑅° =-855.0 𝐾𝐽 𝑚𝑜𝑙 −1 + 537.6 𝐾𝐽 𝑚𝑜𝑙 −1 + 2 × 167.2 𝐾𝐽 𝑚𝑜𝑙 −1 +
17.0𝐾𝐽 𝑚𝑜𝑙 −1

P10.11 Express 𝑎± in terms of 𝑎+ and 𝑎− for (a)

𝐿𝑖2 𝐶𝑂3,(b)CaC𝑙2 , (𝑐)𝑁𝑎3 𝑃𝑂4 , 𝑎𝑛𝑑 (𝑑)𝐾4 𝐹𝑒(𝐶𝑁)6

Assume complete dissociation.

1 1
𝑣
(a) 𝐿𝑖2 𝐶𝑂3:𝑎± = (𝑎++ 𝑎−𝑣− )𝑣 = (𝑎+2 𝑎− )3
1 1
𝑣
(b) CaC𝑙2 : 𝑎± = (𝑎++ 𝑎−𝑣− )𝑣 = (𝑎+ 𝑎−2 )3
1 1
𝑣
(c) 𝑁𝑎3 𝑃𝑂4 : 𝑎± = (𝑎++ 𝑎−𝑣− )𝑣 = (𝑎+3 𝑎− )4
1 1
𝑣
(d) 𝐾4 𝐹𝑒(𝐶𝑁)6: 𝑎± = (𝑎++ 𝑎−𝑣− )𝑣 = (𝑎+4 𝑎− )5
°
P10.12 Calculate ∆𝐺𝑠𝑜𝑙𝑣𝑎𝑡𝑖𝑜𝑛 in aqueous solution for R𝑏 + (𝑎𝑞)using the Born model.
The radius of the R𝑏 + ion is 161 pm.

° 𝑍 2 𝑒 2 𝑁𝐴 1
∆𝐺𝑠𝑜𝑙𝑣𝑎𝑡𝑖𝑜𝑛 = (𝜀 − 1)
8𝜋𝜀0𝑟 𝑟

12 ×′ 602×10−19 𝐶)2 ×𝑁
𝐴 1
−10 𝑚 × (78.5 − 1)
=8𝜋×8.854×10−12𝐶 2 𝐽−1 𝑚𝑜𝑙−1 ×1.61×10
=-426 kj

P10.13 calculate the ionic strength in a solution that is 0.0750 m in

𝐾2 𝑆𝑂4 , 0085 𝑀 𝑖𝑛 𝑁𝑎3 𝑃𝑂4 , 𝑎𝑛𝑑 0,015𝑚 𝑖𝑛 𝑀𝑔𝐶𝑙2
𝑚
𝐼𝐾2 𝑆𝑂4 = (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 )
2

0.0750
= (2 + 4) = 0.225𝑚𝑜𝑙 𝑘𝑔−1
2

𝑚
𝐼𝑁𝑎3 𝑃𝑂4 = (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 )
2

0.0085
= (3 + 9) = 0.051𝑚𝑜𝑙 𝑘𝑔−1
2

𝑚
𝐼𝑀𝑔𝐶𝑙2 = (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 )
2

0.0150
= (4 + 2) = 0.0450𝑚𝑜𝑙 𝑘𝑔−1
2

Total ionic strength

𝐼 = (0.225 + 0.0510 + 0.0450)𝑚𝑜𝑙 𝑘𝑔−1

 =0.321 𝑚𝑜𝑙 𝑘𝑔−1

P10.14 calculate 𝐼 ,𝑦± , and 𝑎± for a 0.0120 m solution of N𝑎3 𝑃𝑂4 at 298 K. Asume
complete dissociation.

N𝑎3 𝑃𝑂4 → 𝑣+ = 3, 𝑣− = 1, 𝑧+ = 1, 𝑧− = 3
𝑚
𝐼= (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 )
2

0.0120
= (3 + 9) = 0.0720𝑚𝑜𝑙 𝑘𝑔−1
2

𝐼
ln𝛾± = −1.173 ∣ 𝑧+ 𝑧− ∣ √𝑚𝑜𝑙 𝑘𝑔−1 = −1.173 × 2 × √0.0720 =

−0.9442

𝛾± = 0.389

𝑚± (𝑣+ +𝑣−) = 𝑚+𝑣 + 𝑚−𝑣−

3
𝑚± = (0.015)2 (0.0075)1 = 5.60 × 10−7

𝑚± =0.0273 𝑚𝑜𝑙 𝑘𝑔−1

𝑚
𝑎± = ( 𝑚±° )𝛾±

𝑎± = 0.0273 × 0.389 = 0.01060

P10.15 Express µ± and µ− for (a) NaCl, (b) MgB𝑟2 , (c) L𝑖3 𝑃𝑂4, and (d)
Ca(N𝑂3 )2. Assume complete dissociation.
µ𝑠𝑜𝑙𝑢𝑡𝑒 𝑣+ µ+ + 𝑣− µ− µ+ +µ−
(a) NaCl: µ± = = =
𝑣 𝑣 2
µ𝑠𝑜𝑙𝑢𝑡𝑒 𝑣+ µ+ + 𝑣− µ− µ+ +µ−
(b) MgB𝑟2 : µ± = = =
𝑣 𝑣 3
µ𝑠𝑜𝑙𝑢𝑡𝑒 𝑣+ µ+ + 𝑣− µ− 3µ+ +µ−
(c) L𝑖3 𝑃𝑂4 : µ± = = =
𝑣 𝑣 4
µ𝑠𝑜𝑙𝑢𝑡𝑒 𝑣+ µ+ + 𝑣− µ− µ+ +2µ−
(d) Ca(N𝑂3 )2. ∶ µ± = = =
𝑣 𝑣 3

P10.17 In the Debye-Hickel theory, the country charge in a spherical shell of

radius r and thickness dr around the central ion of charge +Q is given by -
Q𝑘 2 𝑟𝑒 −𝑘𝑟 𝑑𝑟. Calculate the radius at which the counter charge has its maximum
value, 𝑟𝑚𝑎𝑥 , from this expression. Evaluate 𝑟𝑚𝑎𝑥 for a 0.090 m aqueous solution of
𝑁𝑎3 𝑃𝑂4 at 298 K.
 𝑑(−𝑄𝑘 −2 𝑟𝑒 −𝐾𝑇 )
= −𝑄𝑘 2 𝑒 −𝐾𝑇𝑚𝑎𝑥 + 𝑄𝑘 3 𝑟𝑚𝑎𝑥 𝑒 −𝐾𝑇𝑚𝑎𝑥 = 𝑜
𝑑𝑟

1
-1+𝐾𝑇𝑚𝑎𝑥 = 0; 𝑟𝑚𝑎𝑥 = 𝐾

1 𝑚
= 3.29 × 109 √𝐼 𝑚−1 = 3.29 × 109 × √ 2 (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 )
𝑟𝑚𝑎𝑥

0.090
3.29 × 109 √ (2 × 11 + 1 × 22 ) = 3.29 × 109 × √0.540 𝑚−1 = 2.41 × 109 𝑚−1
2

𝐹𝑚𝑎𝑥 = 4.1 × 10−10 𝑚 = 0.41𝑛𝑚

P10.17 Calculate the solubility of CaC𝑂3(𝐾𝑠𝑝 = 3.4 × 10−9 ) (a) in pure 𝐻2 𝑂 and (b)
in aqueous with 𝐼 = 0.0250 𝑚𝑜𝑙 𝑘𝑔−1 . For part (a) do an iterative calculation of
𝛾±and the solubility until the answer is constant in the second decimal place. Do
you need to repeat this procedure in part (b)?

a. 𝐶𝑎𝐶𝑂3 (𝑠) ⇌ 𝐶𝑎2+ (𝑎𝑞) + 𝐶𝑂32− (𝑎𝑞)

𝑣+ = 1 𝑣− = 1

𝑧+ = 2, 𝑧− = 2
𝑐𝐶𝑎2+ 𝑐𝐶𝑂2−
𝐾𝑠𝑝 = ( )( 3
) 𝛾± = 3.4 × 10−9
𝑐° 𝑐°

𝑐𝐶𝑎2+ = 𝑐𝐶𝑂32−

𝑐𝐶𝑎2+
𝐾𝑠𝑝 = ( ) 𝛾± = 3.4 × 10−9
𝑐°

When 𝛾± = 1 𝑐𝐶𝑎2+ = 5.8 × 10−5 mol 𝐿−1

𝑚
𝐼= ∑(𝑣+ 𝑧−2 + 𝑣− 𝑧−2 )
2

5.8×10−5
= × (4 + 4) = 2.33 × 10−4 mol k𝑔−1
2

ln𝛾± = -1.173× 4 × 4√2.33 × 10−4 = −0.07427

𝛾± = 0.928

When 𝛾± = 0.928𝑐𝐶𝑎2+ = 6.28 × 10−5 mol 𝐿−1

b. 𝐼 = 0.0250 𝑚𝑜𝑙 𝑘𝑔−1

 ln𝛾± = -1.173× 4 × √0.0250 = −0.07427
𝛾± = 0.476
𝑐𝐶𝑎2+ 2
𝐾𝑠𝑝 = ( ° ) × (0.476)2 = 3.4 × 10−9
𝑐
𝑐𝐶𝑎2+ = 1.22 × 10−4 𝑚𝑜𝑙 𝐿−1

There is no need to repeat the calculation because the ionic strength in the solution
is not influenced by the dissociation of the 𝐵𝑎𝑆𝑂4.

P10.18 Calculate the probability of finding an ion at distance greater than 1/k from
the central ion.

∫ 𝑢 𝑑𝑣 = 𝑢𝑣 − ∫ 𝑣 𝑑𝑢
1
𝑙𝑒𝑡 𝑢 = −𝑞𝑘 2 𝑟; 𝑑𝑣 = 𝑒 −𝑘𝑡 𝑑𝑟 𝑣 = − 𝑘 𝑒 −𝑘𝑡 𝑑𝑢 = −𝑞𝑘 2 𝑑𝑟

− ∫ 𝑞𝑘 2 𝑟𝑒 −𝑘𝑡 𝑑𝑟 = 𝑞𝑘𝑟𝑒 −𝑘𝑡 − 𝑞𝑘 ∫ 𝑒 −𝑘𝑡 𝑑𝑟 = 𝑞𝑘𝑟𝑒 −𝑘𝑡 + 𝑞𝑒 −𝑘𝑡

∞ ∞
∫1 𝑞𝑘 2 𝑟𝑒 −𝑘𝑡 ⌊𝑞𝑘𝑟𝑒 −𝑘𝑡 +𝑞𝑒 −𝑘𝑡 ⌋1
1 𝑘 𝑘 0−2𝑞𝑒 −1 2
P(r> 2) = ∞ = ∞ = =9=
∫0 𝑞𝑘 2 𝑟𝑒 −𝑘𝑡 [𝑞𝑘𝑟𝑒 −𝑘𝑡 +𝑞𝑒 −𝑘𝑡 ]0 0−𝑞

0.736

P10.19 Express 𝛾± and 𝛾− for(a) 𝑆𝑟𝑆𝑂4, (b)𝑀𝑔𝐵𝑟2 , (c)𝐾3 𝑃𝑂4 , and (d)𝐶𝑎(𝑁𝑂3 )2 .
Assume complete dissociation.
1
(a) 𝑆𝑟𝑆𝑂4 : 𝛾± = (𝛾+ 𝛾− )2
1
(b) 𝑀𝑔𝐵𝑟2 : 𝛾± = (𝛾+ 𝛾−2 )2
1
(c) 𝐾3 𝑃𝑂4: 𝛾± = (𝛾+3 𝛾− )2
1
(d) 𝐶𝑎(𝑁𝑂3 )2 : 𝛾± = (𝛾+ 𝛾−2 )2

P10.20 calculate the mean ionic molality and mean ionic activity of a 0.105 m
𝐾3 𝑃𝑂4 Solution for which the mean ionic activity coefficient is 0.225.
1 1
𝑣
𝑚± = (𝑣++ 𝑣−𝑣− )𝑣 𝑚 = (31 11 )4 0.105 𝑚𝑜𝑙 𝑘𝑔−1 =
0.239𝑚𝑜𝑙 𝑘𝑔−1
𝑚
𝑎± = ( 𝑚±° ) 𝛾± = 0.239 × 0.225 = 0.0539

P10.21 the equilibrium constant for the hydrolysis of dimethyl lamine.

 (𝐶𝐻3 )2 𝑁𝐻(𝑎𝑞) + 𝐻2 𝑂(𝑎𝑞) → 𝐶𝐻3 𝑁𝐻3+ (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞)

Is 5.12 × 10−4 . Calculate the extent of hydrolysis for (a) a 0.210 m solution of
(𝐶𝐻3 )2 𝑁𝐻 in water using an iterative calculation until the answer is constant in the
second decimal place. (b) Repeat the calculation for a solution that is also 0.500 m
in 𝑁𝑎𝑁𝑂3 . Do you need to use aniterative calculation in this case?

We use an iterative method as explained in the solution to P10.5.

(a) (𝐶𝐻3 )2 𝑁𝐻(𝑎𝑞) + 𝐻2 𝑂(𝑎𝑞) → 𝐶𝐻3 𝑁𝐻3+ (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞)

𝑚 2 2
(
°) 𝑦 ±
𝐾= 𝑚 −4
𝑚 = 5.12 × 10
0.210 − °
𝑚
If 𝑚𝛾± = 1 𝑚 = 1.01 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

When m=1.01 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

𝑚
𝐼= (2) = 𝑚 = 1.01 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1
2

ln𝑚𝛾± = −1.173 × 1 × √1.01 × 10−2 = −0.1180

𝛾± = 0.889

When 𝛾± = 0.889
𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 5.12 × 10−4
0.210− °
𝑚

𝑚 = 1.13 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

We iterate several times.

When 𝑚 = 1.13 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

𝑚
𝐼= (2) = 𝑚 = 1.13 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1
2

ln𝑚𝛾± = −1.173 × 1 × √1.13 × 10−2 = −0.1180

𝛾± = 0.883

When 𝛾± = 0.883
 𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 5.12 × 10−4
0.210− °
𝑚

𝑚 = 1.14 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

The degree of hydrolysis is

0.0114
× 100% = 5.44%
0.210

(b)

𝑁𝑎 + 𝑁𝑂3− 𝑉+ = 1 𝑉− = 1

0.500 0.500 𝑍+ = 1 𝑍− = 1
500
𝐼= (1 + 1) = 0.500 𝑚𝑜𝑙 𝑘𝑔−1
2

Add to this the ionic strength from the last iteration of part (a).

𝐼𝑡𝑜𝑡𝑎𝑙 = 0.500 + 0.0114 = 0.511 𝑚𝑜𝑙 𝑘𝑔−1

ln𝑚𝛾± = −1.173 × 1 × √0.511 = −0.8389

𝛾± = 0.432

𝑚 𝑚 2
( ° )2 𝑦 2 ± ( ° ) (0.432)2
𝐾= 𝑚
𝑚 = 𝑚
𝑚 = 5.12 × 10−4
0.210− ° 0.210− °
𝑚 𝑚

𝑚 = 0.0229 𝑚𝑜𝑙 𝑘𝑔−1

Carrying out another iteration,

𝐼𝑡𝑜𝑡𝑎𝑙 = 0.500 + 0.0227 = 0.523 𝑚𝑜𝑙 𝑘𝑔−1

ln𝑚𝛾± = −1.173 × 1 × √0.523 = −0.8480

𝛾± = 0.428
 𝑚 𝑚 2
( ° )2 𝑦 2 ± ( ° ) (0.432)2
𝐾= 𝑚
𝑚 = 𝑚
𝑚 = 5.12 × 10−4
0.210− ° 0.125− °
𝑚 𝑚

𝑚 = 0.0229 𝑚𝑜𝑙 𝑘𝑔−1

The degree of hydrolysis is

0.0229
× 100% = 10.9%
0.210

P10.22 Dichloroacetic acid has a dissociation constant of 𝐾𝑎 = 3.32 × 10−2 .

Calculate the degree of dissociation for a 0.105 m solution of this acid (a) using the
Debye-Huckel limiting law using an interative calculation until the answer is
constant to within ±2 in the second decimal place. (b) Repeat the calculation
assuming that the mean ionic activity coefficient is one.

We use an iterative method as explained in the solution to P10.5.

(a) We first consider the case when 𝛾 is given by the Debye-Huckel Limiting
law. The concentration of the ionic species is given by

𝑚
( ° )2
𝑚
𝑚 = 3.32 × 10−2
0.105− °
𝑚

𝑚 = 4.47 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

The ionic strength and 𝛾± are given by

𝑚
𝐼= (2) = 𝑚 = 0.0447 𝑚𝑜𝑙 𝑘𝑔−1
2

ln𝑚𝛾± = −1.173 × 1 × √0.0447 = −0.2481

𝛾± = 0.780

We recalculate m and 𝛾± and iterate several times.

𝑚
( ° )2 𝑦 2 ±
𝑚
𝑚 = 3.32 × 10−2 with 𝛾± = 0.780
0.210− °
𝑚

m= 3.32 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

𝑚
𝐼= (2) = 𝑚 = 5.31 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1
2
 ln𝑚𝛾± = −1.173 × 1 × √5.31 × 10−2 = −0.2705

𝛾± = 0.763

When 𝛾± = 0.763
𝑚 2 2
( ) 𝑦 ±
𝑚° −2
𝑚 = 3.32 × 10
0.105 − °
𝑚
m= 5.40 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1
ln𝑚𝛾± = −1.173 × 1 × √5.40 × 10−2 = −0.27246

𝛾± = 0.762

When 𝛾± = 0.762

𝑚 2 2
( ) 𝑦 ±
𝑚° −2
𝑚 = 3.32 × 10
0.105 − °
𝑚
m= 5.40 × 10−2 𝑚𝑜𝑙 𝑘𝑔−1

this is a sufficiently good result, and we calculate the degree of

dissociation to be
0.0540 𝑚𝑜𝑙 𝑘𝑔−1
× 100% = 42.5%
0.105 𝑚𝑜𝑙 𝑘𝑔−1

This result is 9% smaller tham that calculated using the Debye-Huckel

limiting law.

P10.23 Clculate the Debye-Huckel screening 1/k at 298 k in a 0.0075 m solution of

𝐾3 𝑃𝑂4 .

𝐾 = 3.29 × 109 √1𝑚−1

𝑚 0.0075
𝐼= (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 ) = (3 × 11 + 32 ) = 0.045𝑚𝑜𝑙 𝑘𝑔−1
2 2

𝐾 == 3.29 × 10 × √0.045𝑚−1 = 6.98 × 108 𝑚−1

 1
= 1.4 × 10−9 𝑚 = 1.4𝑛𝑚
𝑘

P10.24 Calculate I, 𝛾± and 𝑎± for a 0.0215 m solution of 𝐾2 𝑆𝑂4 at 298 K. how

confident are you that your calculated results will agree with experimental results?
𝑚 1
𝐼= (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 ) = (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 )
2 2

𝑚
𝐼= (2 × 0.0215 𝑚𝑜𝑙 𝑘𝑔−1 + 22 × 0.0215 𝑚𝑜𝑙 𝑘𝑔−1 ) =
2
0.0645 𝑚𝑜𝑙 𝑘𝑔−1

𝐼
ln𝑚𝛾± = −1.173 ∣ 𝑧+ 𝑧− ∣ √𝑚𝑜𝑙 𝑘𝑔−1 = −1.173 × 2 × √0.0645 = −0.5958

𝛾± = 0.551
1 1
𝑣
𝑚± = (𝑣++ 𝑣−𝑣− )𝑣 𝑚 = (22 )3 × 0.0215𝑚𝑜𝑙 𝑘𝑔−1 = 0.1024𝑚𝑜𝑙 𝑘𝑔−1
𝑚
𝑎± = ( 𝑚±° ) 𝛾± = 0.1024 × 0.551 = 0.0564

Not very confident. Figure 10.6 and 10.7 how significant deviations from
predicted behavior for 𝐼 > 0.01𝑚𝑜𝑙 𝑘𝑔−1 .

P10.25 Calculated 𝐼, 𝛾± and 𝑎± for a 0.0175m solution of 𝑁𝑎3 𝑃𝑂4 at 298 K.

assume complete dissociation. How confident are you that your calculated will
agree with experimental results?

𝑁𝑎3 𝑃𝑂4 → 𝑣+ = 3, 𝑧+ = 1, 𝑣− = 1, 𝑧− = 3
𝑚 0.0175
𝐼= (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 ) = (3 + 9) = 0.105𝑚𝑜𝑙 𝑘𝑔−1
2 2

Ln𝑚𝛾± = −1.173 × 3 × √0.105 = −1.1403

𝛾± = 0.320
𝑚
𝑎±= ( 𝑚±° ) 𝛾±

1 1
𝑣
𝑚± = (𝑣++ 𝑣−𝑣− )𝑣 𝑚 = (33 11 )4 0.0175𝑚𝑜𝑙 𝑘𝑔−1 = 0.0399𝑚𝑜𝑙 𝑘𝑔−1
𝑚
𝑎± = ( 𝑚±° ) 𝛾± = 0.0.399 × 0.320 = 0.0128
 Not very confident figure 10.6 and 10.7 show significant deviations from
predicted behavior for 𝐼 > 0.01𝑚𝑜𝑙 𝑘𝑔−1 .

P10.26 Calculated the ionic strength of each of the solutions in problem P10.4.
𝑚
𝐼= (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 )
2

For 𝐶𝑎(𝑁𝑂3 )2
0.0750
𝐼= (1 × 22 + 2 × 12 ) = 0.225𝑚𝑜𝑙 𝑘𝑔−1
2

For NaOH
0.0750
𝐼= (1 + 1) = 0.0750𝑚𝑜𝑙 𝑘𝑔−1
2

For 𝑀𝑔𝑆𝑂4
0.0750
𝐼= (1 × 22 + 1 × 22 ) = 0.300𝑚𝑜𝑙 𝑘𝑔−1
2

For 𝐴𝑙𝐶𝑙3
0.0750
𝐼= (1 × 32 + 3 × 12 ) = 0.450𝑚𝑜𝑙 𝑘𝑔−1
2

P10.27 Calculate the value of 𝑚± in 5.5 x 10−3 molal solutions of (a) KCL, (b)
Ca(𝑁03 )2, and Zn𝑆04 Assume complete dissociation.

(a) KCL
1
𝑣
𝑚± = (𝑣++ 𝑣−𝑣− )𝑣 𝑚
1
𝑚± = (11 11 )2 𝑚 = 5.5 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

(b) Ca(N𝑂3 )2
1
𝑣
𝑚± = (𝑣++ 𝑣−𝑣− )𝑣 𝑚
1 1
𝑚± = (11 22 )3 𝑚 = (4)3 × 5.5 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1 =8.7 ×
10−3 𝑚𝑜𝑙 𝑘𝑔−1

( c) 𝑍𝑛𝑆𝑂4
1
𝑣
𝑚± = (𝑣++ 𝑣−𝑣− )𝑣 𝑚
 1
𝑚± = (11 11 )2 𝑚 = 5.5 × 10−3 𝑚𝑜𝑙 𝑘𝑔−1

P10.28 Calculate ∆𝐻𝑅° and ∆𝐺𝑅° for the reaction Ag𝑁𝑂3 )(𝑎𝑞) + 𝐾𝐶𝐿(𝑎𝑞) →
𝐴𝑔𝐶𝑙(𝑠) + 𝐾𝑁𝑂3 (𝑎𝑞)

∆𝐺𝑅° = ∆𝐺𝑓° (𝐴𝑔𝐶𝑙, 𝑠) + ∆𝐺𝑓° (𝐾 + , 𝑎𝑞) + ∆𝐺𝑓° (𝑁𝑂3− , 𝑎𝑞) − ∆𝐺𝑓° (𝐴𝑔+ , 𝑎𝑞) −
∆𝐺𝑓° (𝑁𝑂3− , 𝑎𝑞) − ∆𝐺𝑓° (𝐾 + , 𝑎𝑞) − ∆𝐺𝑓° (𝐶𝑙 − 𝑎𝑞)

∆𝐺𝑅° = ∆𝐺𝑓° (𝐴𝑔𝐶𝑙2 , 𝑠) − ∆𝐺𝑓° (𝐴𝑔+ , 𝑎𝑞) − ∆𝐺𝑓° (𝐶𝑙 − 𝑎𝑞) = −109.8𝐾𝐽 𝑚𝑜𝑙 −1

−77.1𝐾𝐽 𝑚𝑜𝑙 −1 + 131.2𝐾𝐽 𝑚𝑜𝑙 −1 = −55.7𝐾𝐽 𝑚𝑜𝑙 −1

∆𝐻𝑅° = ∆𝐺𝑓° (𝐴𝑔𝐶𝑙, 𝑠) − ∆𝐺𝑓° (𝐴𝑔+ , 𝑎𝑞) − ∆𝐻𝑓° (𝐶𝑙 − 𝑎𝑞)

∆𝐻𝑅° =-127.0 𝐾𝐽 𝑚𝑜𝑙 −1 − 105.6 𝐾𝐽 𝑚𝑜𝑙 −1 + 167.2 𝐾𝐽 𝑚𝑜𝑙 −1 =

−65.4𝐾𝐽 𝑚𝑜𝑙 −1

P10.29 Calculate the pH of a buffer solution that is 0.200 molal in 𝐶𝐻3 𝐶𝑂𝑂𝐻 and
0.15 molal in 𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 using the Davies equation to calculate 𝛾± . what pH value
would you have calculated if you had assumed that 𝛾± = 1 ?

We write the equilibrium constant in the form

𝛾± 𝑚(𝐶𝐻3 𝑂 + ) 𝛾± 𝑚(𝐶𝐻3 𝐶𝑂𝑂 − )

𝐾= 𝑚(𝐶𝐻3 𝐶𝑂𝑂)

( 𝛾± )2 𝑥×(0.150+𝑥) 0.150
1.75 × 10−5 = = 0.200 ( 𝛾± )2 𝑥
(0.200−𝑥)

0.200 1.75×10−5
𝑚(𝐶𝐻3 𝑂+ ) = 0.150 × ( 𝛾± )2

𝑝𝐻 = 𝑙𝑜𝑔𝑚{𝑚(𝐻3 𝑂+ )}

To calculate 𝛾± from the Davies equaton, we must first calculate the ionic strength
of the solution. The small value of K tells us the degree of ionization of the acetic
acid is small so that the ionic strength can be calculated from the concentration of
𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 alone.

𝑚 0.150 𝑚𝑜𝑙 𝑘𝑔−1

𝐼= (𝑣+ 𝑧−2 + 𝑣− 𝑧−2 ) = × (1 + 1) = 0.150𝑚𝑜𝑙 𝑘𝑔−1
2 2
Using the Davies equation

1 1⁄2
( °) 1
𝑙𝑜𝑔10 Υ± = −0,51|𝑧+ 𝑧− | [ 𝑚 ⁄
− 0.30 ( )]
1 12 𝑚°
1 − ( °)
𝑚

(0.150)1⁄2
= −0,51 [ − 0.30 × 0.150] = −0.1194
1 − (0.150)1⁄2

Υ± = 0.760

4)
0.200 1.75 × 10−5
𝑚(𝐻3 𝑂 = × = 4.04 × 10−5 𝑚𝑜𝑙𝐾𝑔−1
0.150 (0.760)2

𝑝𝐻 = −𝑙𝑜𝑔{4.04 × 10−5 } = 4.39

If we had assumed Υ± = 1

0.200 1.75 × 10−5

𝑚(𝐻3 𝑂4 ) = × = 2.33 × 10−5
0.150 (Υ± )2

𝑝𝐻 = −𝑙𝑜𝑔{2.33 × 10−5 } = 4.63

P10.30 Use Dvies equation to calcule Υ± for a 1.00 molar solution of KOH.
Compare your answer with the values in Table 10,3-

1 1⁄2
( °) 1
𝑙𝑜𝑔10 Υ± = −0,51|𝑧+ 𝑧− | [ 𝑚 ⁄
− 0.30 ( )]
1 12 𝑚°
1 − ( °)
𝑚

(0.100)1⁄2
= −0,51 [ − 0.30 × 1.00] = −0.1020
1 − (1.00)1⁄2

Υ± = 0.791

This answer is reasonably close to the tabulated value of 0.0756