ENVE 102 ENVIRONMENTAL CHEMISTRY

2022-2023 SPRING SEMESTER

RECITATION 5

Question 1:

An aqueous solution of 10-2 M of HNO2 (nitrous acid), a weak acid, with Ka = 4x10-4, is prepared.
Please write all the necessary equations according to the methodology developed in class. Do not
solve the problem.

a. all relevant chemical reactions,

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

Answer 1:

a. All relevant chemical reactions

HNO2+ H2O ↔ NO2- + H3O+ Ka = 4x10-4

2H2O ↔ H3O+ + OH- Kw = 10-14

b. List all the species,

HNO2, NO2-, H3O+, OH-, (H2O) (H2O is in parenthesis because we will not find its conc.)
we have 4 unknowns so we will need 4 equations to solve
c. equilibria expressions,
[H3 O+ ][NO−2]
𝐾𝐾𝑎𝑎 = = 4𝑥𝑥10−4
[HNO2 ]

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

d. mass balance equation,

CT, NO2 → [NO2-]+ [HNO2] = 10-2 M

e. proton condition

PRL: HNO2, H2O

> PRL: H3O+
< PRL: NO2-, OH-

[NO2-]+ [OH-] = [H3O+]

f. charge balance,

[NO2-]+ [OH-] = [H3O+]

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 Here in the nitrous acid question, the proton condition and the charge balance are the
same. This is not always going to be the case. So, do not memorize or prefer one equation
over the other just yet. We will see many cases where one would be more advantageous
than the other.

Question 2:
An aqueous solution of 10-4 M of NaCN, (sodium cyanide) salt of a weak acid is prepared. Ka
for HCN is 4.8x10-10. Please write all the necessary equations according to the methodology
developed in class. Do not solve the problem.

a. all relevant chemical reactions,

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

Answer 2:

a. All relevant chemical reactions

NaCN → Na+ + CN- salt, completely ionized in water and forms the
conjugate base of a weak acid HCN
CN-+ H2O ↔ HCN + OH- Kb
2H2O ↔ H3O+ + OH- Kw = 10-14
b. make the species list,
Species: Na+, CN-, HCN, OH-, H3O+, (H2O) 5 unknowns so we need 5 independent
eqns.
c. equilibria expressions,
[𝑂𝑂𝑂𝑂 − ][𝐻𝐻𝐻𝐻𝐻𝐻 ]
𝐾𝐾𝑏𝑏 =
[𝐶𝐶𝐶𝐶 − ]
𝐾𝐾𝑤𝑤 = [𝐻𝐻3 𝑂𝑂+ ][𝑂𝑂𝑂𝑂 − ] = 10-14
𝐾𝐾𝑤𝑤 = 𝐾𝐾𝐾𝐾 ∗ 𝐾𝐾𝐾𝐾 = 10-14
[10−14 ]
𝐾𝐾𝑏𝑏 = = 10-4.7 = 2.1x10-5
[4.8∗10−10 ]
*
You can also write 2.1x10-5 as the value of Kb. You should be at ease to make all such
calculations (convert Kb into pKb, etc.) using your calculator.
d. mass balance equation,

*We have two foreign species that cannot come from H2O. These are Na+ and CN-,
therefore we write two separate mass balances.

M.B. CT, Na → [Na+] = 10-4 M

CT, CN → [HCN] + [CN-] = 10-4 M
e. proton condition

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 PRL: CN-, H2O (Since NaCN completely dissociates & Na+ does not react with H+/OH-)
> PRL: H3O+, HCN
< PRL: OH-
[OH-] = [H3O+]+[HCN]

f. charge balance,

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

As you see in this case, the proton condition and charge balance are quite different from each
other. PC has a smaller number of species in it – which might be an advantage when solving
questions. We will see this next week.

Question 3: An aqueous solution of 10-4 M of Na2CO3, salt of carbonic acid is prepared. You need
to consider all relevant reactions. Please write all the necessary equations according to the
methodology developed in class.

a. all relevant chemical reactions,

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

Answer 3:

a. all relevant chemical reactions,

Na2CO3 → 2 Na+ + CO32-
CO32- + H2O ↔ HCO3- + OH- Kb2 = 2x10-4 (10-3.7)
HCO3- + H2O ↔ H2CO3 + OH- Kb1 = 2x10-8 (10-7.7)
2H2O ↔ H3O+ + OH- (Kw)

b. write the species list,

Na+, HCO3-, CO32-, H3O+, H2CO3, OH-, (H2O) 6 unknowns, so we need 6 independent
eqns.

c. equilibria expressions,

[𝑂𝑂𝑂𝑂 − ][𝐻𝐻𝐻𝐻𝐻𝐻3 − ]
2x10-4 = [𝐶𝐶𝐶𝐶3 2− ]

[𝐻𝐻2 𝐶𝐶𝐶𝐶3 ][𝑂𝑂𝑂𝑂 − ]

2x10-8 = [𝐻𝐻𝐻𝐻𝐻𝐻3 − ]

𝐾𝐾𝑤𝑤 = [𝐻𝐻3 𝑂𝑂+ ][𝑂𝑂𝑂𝑂 − ] = 10-14

d. mass balance equation,

CT, Na ⇒ [Na+] = 2 * 10-4 M

CT, CO32⇒ [H2CO3] + [HCO3-] + [CO32-] = 10-4 M
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 e. proton condition

PRL: CO32-, H2O

>PRL: H2CO3 (beware! 2 more protons with respect to the PRL), HCO3-, H3O+
<PRL: OH-
2 [H2CO3] + [HCO3-] + [H3O+] = [OH-]
The coefficient in the PC indicates how many protons less/more than the PRL specie.
f. charge balance

[HCO3-] + 2[CO32-] + [OH-] = [H3O+] + [Na+]

The coefficient in the CB indicates how many charges per mole the specie introduces
into the solution, i.e. coefficient in the CB directly comes from the charge of the specie.

Solution of multiprotic acids with “hand calculation” is quite tedious, so we will learn how to
solve them graphically in a few weeks time.

Question 4: An aqueous solution of 7*10-3 M of KOH, a strong base is prepared. You need to
consider all relevant reactions. Please write all the necessary equations according to the
methodology developed in class.

a. all relevant chemical reactions,

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

Answer 4:

a. all relevant chemical reactions,

KOH → K+ + OH Kb=0.316 (a large number indicating that this base ionizes
completely. Therefore we will not deal with Kb or any
equilibrium expression for KOH. We just write a single
sided arrow as you see and KOH will completely finish.)
+ -
2H2O ↔ H3O + OH Kw =10-14

b. write the species list,

K+, OH-, (H2O) 2 unknowns, so we need 2 independent eqns.

c. equilibria expressions,

𝐾𝐾𝑤𝑤 = [𝐻𝐻3 𝑂𝑂+ ][𝑂𝑂𝑂𝑂 − ] = 10-14 note that we do not include Kb since strong base goes

through complete ionization

d. mass balance equation,

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 CT, K+ ⇒ [K+] = [OH-] = 7 * 10-3 M (note KOH does not exist in solution @ equilibrium)

e. proton condition

PC equals to CB when the base/acid is strong. Let’s continue and write CB in part f.

f. charge balance

[OH-] = [H3O+] + [K+]

The coefficient in the CB indicates how many charges per mole the specie introduces
into the solution, i.e. coefficient in the CB directly comes from the charge of the specie.