ENVE 102 ENVIRONMENTAL CHEMISTRY

2019-2020 SPRING SEMESTER

RECITATION #7

Question 1: An aqueous solution of 10-2 M NH4Cl is prepared. Use the methodology

developed in class to solve for the pH and the concentrations of all species at equilibrium
(Ka of NH4+ is 10-9.3).

Question 2: H3X is a weak triprotic acid. For 10 -5 M solution of Na2HX, answer parts (a)
through (f): (Note that the weak triprotic acid H3X has Ka1 of 3x10-3, Ka2 of 7x10-7, Ka3 of
3.2x10-12.)

a. all relevant chemical reactions,

b. species list,
c. equilibria expressions,
d. mass balance equation,
e. charge balance,
f. proton condition

Question 3: 10-4 mole of Lithium hydroxide (LiOH) is added into 1 L water. Calculate
equilibrium concentrations of all species using pC-pH diagram.
 ENVE 102 ENVIRONMENTAL CHEMISTRY
2019-2020 SPRING SEMESTER
RECITATION #7 ANSWER KEY

Question 1: An aqueous solution of 10-2 M NH4Cl is prepared. Use the methodology

developed in class to solve for the pH and the concentrations of all species at
equilibrium (Ka of NH4+ is 10-9.3).

(𝑁𝐻4 𝐶𝑙 ) → 𝐶𝑙 − + 𝑁𝐻4 +
𝑁𝐻4 + + 𝐻2 𝑂 ↔ 𝑁𝐻3 + 𝐻3 𝑂+ Ka=10-9.3
2𝐻2 𝑂 ↔ 𝐻3 𝑂+ + 𝑂𝐻 − Kw = 10-14

Species list: 𝐶𝑙 − , 𝑁𝐻4 + , 𝐻3 𝑂+ , 𝑂𝐻 − , 𝑁𝐻3 , (𝐻2 𝑂)

MB

𝐶𝑇,𝐶𝑙 − = [𝐶𝑙 − ] = 10−2 𝑀

𝐶𝑇,𝑁𝐻3 = [𝑁𝐻4 + ] + [𝑁𝐻3 ] = 10−2 M

EQ

𝐾𝑤 = [𝐻3 𝑂+ ][𝑂𝐻− ] = 10−14

[𝑁𝐻3 ][𝐻3 𝑂+ ]
𝐾𝑎 = = 10−9.3
[𝑁𝐻4 + ]

CB

[𝑁𝐻4 + ] + [𝐻3 𝑂+ ] = [𝐶𝑙 − ] + [𝑂𝐻− ]

PC

𝐻3 𝑂+ 𝑁𝐻3
𝑃𝑅𝐿 − 𝐻2 𝑂 𝑁𝐻4+
𝑂𝐻 −

[𝑁𝐻3 ] + [𝑂𝐻 − ] = [𝐻3 𝑂+ ]

So you see here the CB and PC are quite different from each other. Also, the CB has
more species when compared to the PC. So it will be more advantageous to use the
PC during making assumptions and solving for unknown specie concentrations.

Assumption-1 on the MB

C=10-2 M and Ka=10-9.3 M

[𝑁𝐻4 + ] ≫ [𝑁𝐻3 ]
𝑀𝐵 𝑏𝑒𝑐𝑜𝑚𝑒𝑠 [𝑁𝐻4 + ] = 10−2 M

Assumption-2 – acidic or basic soln

[𝐻3 𝑂+ ] ≫ [𝑂𝐻− ]
[𝑁𝐻4 + ] + [𝑁𝐻3 ] = [𝐶𝑙 − ] + [𝑂𝐻− ] 𝐔𝐒𝐄𝐋𝐄𝐒𝐒
The reason the CB is useless is because [Cl-] and [NH4+] concentrations are equal to
each other, but [NH3] and [OH-] are not! So we can’t make any assumption that will
be useful and easy for us. However, we have the PC and it contains only three
species, so it will be a lot more logical and easier to make assumptions on it.

So we use the PC
[𝑁𝐻3 ] + [𝑂𝐻 − ] = [𝐻3 𝑂+ ]
[𝑁𝐻3 ] ≫ [𝑂𝐻− ]
[𝑁𝐻3 ] = [𝐻3 𝑂+ ]

[𝑁𝐻3][𝐻3𝑂+ ]
𝐾𝑎 = + = 10−9.3
[𝑁𝐻4 ]
[𝐻3𝑂+ ][𝐻3𝑂+ ]
= 10−9.3
10−2
[𝐻3𝑂+ ] = (10−5.65 ) M
[𝑂𝐻− ] = (10−8.35 ) M
[𝑁𝐻3 ] = (10−5.65 ) M
𝑝𝐻 = −𝑙𝑜𝑔[𝐻3 𝑂+ ] = −𝑙𝑜𝑔(10−5.65 ) = 5.65

Check assumption

Assumption 1
[𝑁𝐻4 + ] ≫ [𝑁𝐻3 ]
[𝑁𝐻4 + ] + [𝑁𝐻3 ] = 10−2 M

10−2 + 10−5.65 =? 10−2

10−5.65
∗ 100 <? 5%  Yes, assumption holds.
10−2

Assumption 2

[𝑁𝐻3 ] + [𝑂𝐻 − ] = [𝐻3 𝑂+ ]

[𝑁𝐻3 ] ≫ [𝑂𝐻− ]

10−5.65 + 10−8.35 =? 10−5.65

10−8.35
∗ 100 <? 5%  Yes, assumption holds.
10−5.65

[𝐻3𝑂+ ] = (10−5.65 ) M
[𝑂𝐻− ] = (10−8.35 ) M
[𝑁𝐻3 ] = (10−5.65 ) M
[𝑁𝐻4 + ] = 10−2 M
𝑝𝐻 = −𝑙𝑜𝑔[𝐻3 𝑂+ ] = −𝑙𝑜𝑔(10−5.65 ) = 5.65

Question 2: H3X is a weak triprotic acid. For 10 -5 M solution of Na2HX, answer parts (a)
through (f): (Note that the weak triprotic acid H3X has Ka1 of 3x10-3, Ka2 of 7x10-7, Ka3 of
3.2x10-12.)

a. all relevant chemical reactions,

b. species list,
c. equilibria expressions,
d. mass balance equation,
e. charge balance,
f. proton condition

a)
All relevant chemical reactions

Na2HX 2Na+ + HX2- (salt: dissociates completely)

HX2- + H2O ⇆ X3- + H3O+ Ka3 = 3.2x10-12
HX2- + H2O ⇆ H2X- + OH- Kb2 = Kw / Ka2= (10-14 / 7x10-7) = 1.43x10-8
H2X- + H2O ⇆ H3X + OH- Kb1 = Kw / Ka1= (10-14 / 3x10-3) = 3.33x10-12
2H2O ⇆ H3O+ + OH- Kw = 10-14

b) List of species

Na2HX (complete dissociation), Na+, H3X, H2X-, HX2-, X3-, (H2O), H3O+, OH-

c) Equilibria expressions

[𝑋 3− ][ 𝐻3 𝑂+ ]
𝐾𝑎3 = = 3.2𝑥10−12
[ 𝐻𝑋 2− ]
[𝐻2 𝑋 − ][𝑂𝐻− ]
𝐾𝑏2 = = 1.43𝑥10−8
[ 𝐻𝑋 2− ]
[𝐻3 𝑋][𝑂𝐻− ]
𝐾𝑏1 = −
= 3.33𝑥10−12
[ 𝐻2 𝑋 ]
Kw = [H3O+][OH-] = 10-14

d) Mass balance equations

C T,Na+ = [Na+] = 2x10-5 M

C T,X3- = [H3X] + [H2X-]+ [HX2-] + [X3-] = 10-5 M

e) Charge balance

[Na+] + [H3O+] = [H2X-] + 2[HX2-] + 3[X3-] + [OH-]

f) Proton condition

PRL= HX2-, H2O

 >PRL:
H3O+ (1 proton more than PRL)
H2X- (1 proton more than PRL)
H3X (2 protons more than PRL)
<PRL:
X3- (1 proton less than PRL)
OH- (1 proton less than PRL)

2[H3X] + [H2X-] + [H3O+] = [X3-] + [OH-]

Question 3: 10-4 mole of Lithium hydroxide (LiOH) is added into 1 L water. Calculate
equilibrium concentrations of all species using pC-pH diagram

Solution is on YouTube.

Part 1 – Drawing the Summation Line

https://youtu.be/VnFjgbadCb0

Part 2 – Checking the Intersection Points (Easier Method)

https://youtu.be/-WTxwfZPnnM