ENVE

– 102
Recitation #6
06.04.2015
Question 1) Hydrocyanic acid (HCN) is a weak monoprotic acid with a Ka of 10-9.3. Find the
pH and all specie concentrations for a 10-3 M solution of this acid.
Answer 1.
a) All relevant chemical reactions
HCN + H2O ⇆ CN- + H3O+ Ka
2H2O ⇆ H3O+ + OH- Kw
b) Species present in the system
HCN, CN-, H3O+, OH-, H2O

We have 4 unknowns, so we need to develop 4 equations to solve the question

c) Equilibria expressions
[𝐶𝑁 " ][𝐻# 𝑂$ ]
𝐾! = = 10"%.#
[𝐻𝐶𝑁]

Kw= [H3O+][OH-] = 10-14

d) Mass balance equations

CT, CN-= [CN-] + [HCN] = 10-3 M

e) Charge balance
Charged species: CN-, H3O+, OH-

[H3O+] = [OH-] + [CN-]

f) Proton condition
Proton reference level (PRL): HCN; H2O

>PRL: H3O+
<PRL; OH-, CN-

[H3O+] = [OH-] + [CN-]

Assumption 1:

Consider the mass balance equation

CT, CN = [CN-] + [HCN] = 10-3 M

According to the generalizations made, we see in this case that 10-3>> Ka, therefore
Assume [HCN] >> [CN-], so we can neglect [CN-], then [HCN] becomes:

[HCN] = 10-3 M

Assumption 2:

Consider the proton condition/charge balance equation (they are the same for this
condition)

[H3O+] = [OH-] + [CN-]

We are adding an acid into water, hence we expect the solution to be acidic.

Assume [H3O+] >> [OH-], so we can neglect [OH-]

[H3O+] = [CN-]

Solve the problem using your assumptions

• Take Ka equation

[𝐶𝑁 " ][𝐻# 𝑂$ ]

𝐾! = = 10"%.#
[𝐻𝐶𝑁]
We know here the value of [HCN]. Also we know that [CN-] = [H3O+]

[𝐻# 𝑂$ ]'
= 10"%.#
10"#
[𝐻# 𝑂$ ]' = 10"('.#

[H3O+] = 10-6.15 M = 7.08 * 10-7 M

[H3O+] = [CN-] = 10-6.15 M = 7.08 * 10-7 M

We need to find also the concentration of OH-. Take water equilibrium reaction

Kw= [H3O+][OH-] = 10-14

10"() 10"()
[𝑂𝐻" ] = = = 10",.-+ 𝑀 = 1.41 ∗ 10"- 𝑀
[𝐻# 𝑂$ ] 10"*.(+

Check your assumptions!!!

Assumption 1 check

M.B.;

CT, CN- = [CN-] + [HCN] = 10-3 M

HCN >> CN-

10-3 >> 10-6.15

Error: (10-6.15 /10-3)*100 = 0.07% Assumption is correct

Assumption 2 check

P.C.;

[H3O+] = [OH-] + [CN-]

[H3O+] >> [OH-]

10-6.15 >> 10-7.85

Error: (10-7.85/10-6.15)*100 = 1.99 % (error is < 5%), so assumption is correct

Find pH and pOH

pH= -log [H3O+]

= - log (10-6.15)

pH = 6.15 and pOH = 7.85

Final step: Write all the concentrations you calculated.

[OH-] = 10-7.85 M

[H3O+] = [CN-]= 10-6.15 M

[HCN] = 10-3 M

Question 2) Determine the total concentration of NH3 and also the concentration of all the
species in a solution where NH3 is added into water. The pH of the solution is 10. (Kb = 10-
4.7)

Answer 2.
a) All relevant chemical reactions
NH3 + H2O Û NH4+ + OH- Kb
2H2O Û H3O+ + OH- Kw
b) Species present in the system
NH3, NH4+, H2O, OH-, H3O+
We have 3 unknowns (including OH- which can be solved instantly by Kw due to given H3O+
concentration); so we need to have 3 equations to solve the question.
c) Equilibria expressions
[𝑂𝐻" ][𝑁𝐻)$ ]
𝐾. = = 10").,
[𝑁𝐻# ]

Kw = [H+]*[OH-] = 10-14
d) Mass balance equation
CT, NH3 = [NH4+] + [NH3] = ??? M
e) Charge balance
Charged species: NH4+, OH-, H3O+
[NH4+] + [H3O+] = [OH-]
f) Proton condition
PRL: NH3, H2O



P.C: [NH4+] + [H3O+] = [OH-]
Start solving the equations

We have;
pH = 10
-log[H3O+] = 10
[H3O+] =10-10 M
[OH-] = Kw / [H3O+] = 10-14 / (10-10) =10-4 M
Use Proton Condition/Charge Balance

[NH4+] + [H3O+] = [OH-]

[NH4+] + 10-10 =10-4
[NH4+] =10-4 M
Use Kb

[𝑂𝐻" ][𝑁𝐻)$ ]
𝐾. = = 10").,
[𝑁𝐻# ]

10") ∗ 10")
= 10").,
[𝑁𝐻# ]

[NH3] = 10-3.3 M
Total concentration of NH3 species

CT,NH3 = [NH4+] + [NH3] = 10-4 M + 10-3.3 M = 6.01*10-4 M

Note that we were able to solve the question without making any assumptions, because
one of the unknowns [OH-] was solved instantly and the unknown number dropped to 2.
We had enough equations to solve for the remaining unknowns in the question without
needing any assumptions.

Final step: Write all the concentrations you calculated.

[H3O+] = 10-10 M

[OH-] = [NH4-]= 10-4 M [NH3] = 10-3.3

Question 3: Find the pH of a 10-1 M sodium formate (HCOONa) solution (Ka= 10-3.75) by
using;
a) No assumptions,
b) Two assumptions,
c) One assumption.
Note that sodium formate is the salt of weak monoprotic formic acid (HCOOH)
Answer 3.
a) All relevant chemical reactions
HCOONa → Na+ + HCOO-
HCOO- + H2O ⇆ HCOOH + OH- Kb
2H2O ⇆ H3O+ + OH- Kw
b) Species present in the system
Na+, HCOO-, HCOOH, H2O, H3O+, OH-
We have 5 unknowns (including Na), so we need 5 equations to solve the question
c) Equilibria expressions
[𝑂𝐻" ][𝐻𝐶𝑂𝑂𝐻]
𝐾. = = 10"(/.'+
[𝐻𝐶𝑂𝑂" ]
Kb = 10-14/10-3.75 = 10-10.25 = 5.62*10-11
Kw= [H3O+][OH-] = 10-14
d) Mass balance equations
CT, HCOO- = [HCOO-] + [HCOOH] = 10-1 M
CT, Na+ = [Na+] = 10-1 M
e) Charge balance
Charged species: Na+, HCOO-, H3O+, OH-
[Na+] + [H3O+] = [HCOO-] + [OH-]
f) Proton condition
PRL: HCOO-, H2O

P.C.; [H3O+] + [HCOOH] = [OH-]

Solve the problem using
a) No assumption
Try to convert/write everything in terms of the [H3O+] or [OH-] ions.
[𝑂𝐻" ][𝐻𝐶𝑂𝑂𝐻]
𝐾. = = 10"(/.'+
[𝐻𝐶𝑂𝑂" ]

[1233"]
[HCOOH]= 10-10.25* [31"]

[HCOO-] + [HCOOH] = 10-1 M (mass balance equation)
[HCOO-] = 10-1 - [HCOOH]
Insert this equation into Kb;
((/!" " [78997])
[HCOOH]= 10-10.25 * [31 ! ]

[HCOOH] ∗ [𝑂𝐻" ] = 10"(/.'+ ∗ (10"( − [HCOOH])

[HCOOH] ∗ [𝑂𝐻" ] = 10"((.'+ − 10"(/.'+ [HCOOH]
[HCOOH]([𝑂𝐻" ] + 10"(/.'+ ) = 10"((.'+

10"((.'+
[HCOOH] =
[𝑂𝐻" ] + 10"(/.'+
Write H3O+ in terms of OH-
[H3O+] = 10-14/[OH-]

Insert these equations into P.C.;
[H3O+] + [HCOOH] = [OH-]
10"() 10"((.'+
+ = [𝑂𝐻" ]
[𝑂𝐻" ] [𝑂𝐻" ] + 10"(/.'+

[OH-] = x M
x3 + 10-10.25x2 - 5.63*10-12x - 5.62*10-25= 0
x = 2.37*10-6 M = [OH-] (from calculator)
[H3O+] = 10-14/(2.37*10-6) = 4.22*10-9 M
pH = - log(4.22*10-9) = 8.37

b) Two assumptions
Assumption 1: From mass balance
CT, HCOO- = [HCOO-] + [HCOOH] = 10-1 M
Assume [HCOO-]>> [HCOOH] so,
[HCOO-] = 10-1 M

Assumption 2: From P.C.
We make the assumption using the PC, because charge balance has two terms on
either side and is not helpful.
[H3O+] + [HCOOH] = [OH-]
[HCOOH] >> [H3O+] because we expect a basic solution ([H3O+] < 10-7M)
[OH-] = [HCOOH]

Solve the problem
From Kb;

[𝑂𝐻" ][𝐻𝐶𝑂𝑂𝐻]
𝐾. = = 10"(/.'+
[𝐻𝐶𝑂𝑂" ]
Assumptions: [OH-] = [HCOOH] and [HCOO-] = 10-1 M
 [𝑂𝐻" ][𝑂𝐻" ]
𝐾. = = 10"(/.'+
[10"( ]

Kb = [OH-]2=10-11.25
[OH-] = 2.37*10-6 M = [HCOOH]
From Kw;
Kw= [H3O+][OH-] = 10-14
[H3O+] =4.22*10-9 M
pH = 8.38
Assumption check
Check mass balance assumption
CT, HCOO- = [HCOO-] + [HCOOH] = 10-1 M
10-1 + 2.37*10-6 =10-1
Error: (2.37*10-6/10-1)*100 = 0.00237 % so assumption is correct. Since there is almost
5 orders of magnitude difference, you do not have to calculate the error.
Check Proton condition assumption
P.C. [H3O+] + [HCOOH] = [OH-]
4.22*10-9 + 2.37*10-6 =2.37*10-6
Error: (4.22*10-9/2.37*10-6)*100 = 0.18% so assumption is correct

c) One assumption
Assumption 1:
[OH-] >> [H3O+] we expect basic solution.
From P.C.
[H3O+] + [HCOOH] = [OH-]
[HCOOH] = [OH-] = x M
[H3O+] = (10-14 / x) M
From mass balance;
CT, HCOO- = [HCOO-] + [HCOOH] = 10-1 M
[HCOO-] = (10-1 – x) M

From Kb;
𝑥'
𝐾. = = 10"(/.'+
[10"( − 𝑥]
x2 +10-10.25x - 10-11.25 = 0
"." √. # ")!< ".$ √. # ")!<
x1 = '!
, x2 = '!

a = 1, b = 10-10.25, c = -10-11.25
x = 2.37*10-6 M =
[OH-] = [HCOOH] = 2.37*10-6 M
[HCOO-] =10-1 - x = 0.0999 M
[H3O+] = 10-14/x = 4.22x10-9 M
pH = -log [H3O+] = 8.37

Assumption check:
P.C.;
[H3O+] + [HCOOH] = [OH-]
4.22*10-9 + 2.37*10-6 = 2.37*10-6
Error: (4.22*10-9 / 2.37*10-6)*100 = 0.178 % so assumption is correct

Final step: Write all the concentrations you calculated.

[OH-] = [HCOOH] = 2.37*10-6 M

[H3O+] = 4.22x10-9 M
[HCOO-] = 10-1 M

[Na+] = 10-1 M

Note that the determined concentrations are the same in all three solutions. Only the
time it takes to reach the solution is different for each!