THE COPPERBELT UNIVERSITY

SCHOOL OF MATHEMATICS AND NATURAL SCIENCES

CHEMISTRY DEPARTMENT

NAME: BERNARD NZEKA

SIN: 19137843

PROGRAM: BSc CHEMISTRY

COURSE: CH 491

TASK: ASSIGNMENT 4

LECTURER: MR. HAYUMBU

DUE DATE: 28TH JULY, 2023 @ 14HRS

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QUESTION ONE (Freshwater Chemistry) [76 Marks]

(a) Various relationships between ionic strength and activity coefficients have been
developed. Write the expressions for the named relationships in the table below
and the concentration ranges that they apply if possible. [10]

I and i
Relationship Equation for 2 marks per cell Use concentration range
name
Debye-Huckle log γ i=−0. 5 z i √ I -5 -2.3
2
10 - 10 M [1]
(DH) equation

(( )
Extended √I -2.3 -1
log γ i=−0. 5 z 2i 10 - 10 M [1]
Debye-Huckle
equation 1+ 0.33 ai √ I )

When a number of ions are

Güntelburg
approximation
log γ i=−0. 5 z √I 2
i
( 1+ √ I ) ( ) present in solution (10
1
M)
-2.3 -
-10

(( )
Truesdell- √I -
log γ i=−0. 5 z 2i −bI
Jones equation 1+ 0.33 ai √ I )

( )
Davies √ I −bI Monovalent, I=0.1-0.7M
log γ i=−0. 5 z 2i Divalent, I= 0.1- ~ 0.3M
equation ( 1+ √ I )

(b) Explain the terms congruent and incongruent dissolution [2]. Using quartz and
sodium feldspars to give examples of congruent and incongruent dissolution
reactions, respectively [6]
Answer:

Congruent dissolution occurs where aqueous phase solutes are the only products.
Example: Congruent dissolution of quartz:

0
SiO2 (s )+ 2 H 2 O ⇌ Si ( OH )4 (aq ) @ pH<9
Quartz Silicic acid

Incongruent dissolution occurs where new solid phase(s) and aqueous phase solutes
are the products.
Example: Incongruent dissolution of Na-feldspar

+¿+9 H2 O ⇌ ¿ +¿ ¿
2 NaAl Si 3 O 8(s) +2 H Al2 Si 2 O5 ( OH )4 (s) +2 Na(aq)+4 Si ( OH )04 (aq )
Na-feldspar Kaolinite Silicic acid

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(c) For a weak acid such as trichlorophenol (TCP), write the acid-conjugate base
equilibrium reaction [1] and equilibrium expression [1]. Follow-up these
equations by explaining the term analytical activity [2] and give the expression
for analytical activity. [1]
Answers:
C6H2Cl3OH ⇌ C6H2Cl3O- + H+

K=¿ ¿

Analytical activity, is equal to the sum of the equilibrium activities of the acid
and its conjugate base.

C = {HA} + {A-}

(d) Write the three terms for alkalinity encountered in CH 491 [3] and explain why
the parameter is important [2].
(i) ¿
(ii) ¿
(iii) ¿
(iv) It is important because it is used in assessing the effects of environmental
change on aqueous systems.
(e) Figures A and B below were encountered under the topic of species distribution
in freshwaters in CH 491. Answer the three questions on them [10].

(i) Give an overall title suitable for both figures. [1]

ANSWER: pH dependence of metal complexation reactions

Figure A: Figure B:

(ii) In PEC/the notes, the figures (A & B) actually have related subtitles, state
them [2].
ANSWER:
Figure A Title: Plot of -log{ } against pH
Figure B Title: a plot of mole fraction, ꭓ, against pH.
(iii) Explain the difference between the two diagrams [3]
ANSWER: The observed difference the two graphs is, figure A is a plot
of – log{ }against pH on the other hand figure B is a plot
mole fraction, ꭓ, against pH.

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 (iv)Complete the second column of the table below for each species [5]
Species Optimum pH value or range
3+¿ ¿
1. Cr 1
2+¿ ¿
2. Cr (OH ) 4-6
+¿¿
3. Cr (OH )2 6
0
4. Cr (OH )3 8-10
−¿ ¿
5. Cr (OH )4 11

(i) What type of chemical reaction that generates these species [2]
ANSWER: Hydrolysis Reaction

(ii) Write the four reactions that general the 2nd to the 5th species [4]
ANSWER:
(a) Cr3+ + H2O ⇌ CrOH2+ + H+
+¿¿
(b) Cr3+ + 2H2O ⇌ Cr(OH )2 + 2H+
(c) Cr3+ + 3H2O ⇌ Cr(OH )O3 + 3H+
−¿¿
(d) Cr3+ + 4H2O ⇌ Cr(OH )4 + 4H+

(f) Explain what is meant by a redox-sensitive element [2] and give three examples
of redox-sensitive elements found in the Katanga Basin of North-Western,
Copperbelt and Luapula Provinces of Zambia. [3] Slides 83 and 84.
ANSWER:
Definition - Redox-sensitive elements are which can exist in more than one
oxidation state in natural waters.

Three examples in the Katanga Basin are

(i) Uranium
(ii) Plutonium
(iii) Neptunium

(g) pε –pH diagrams describe redox equilibria as shown in the figure (Slide 92)
below.
pε and pH Relationships: pε – pH graph for As-H2O

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 (i) Fill in the numbered blanks of two statements below relating to redox
equilibria. Slide 89.

For any system, stability relationships between solution phase species (1) and
solid phases (2) can be used to construct pε –pH diagrams representing species
distribution (3) with the upper and lower stability limits of water.[3]
Generally, the relationship between pε and pH for redox equilibria involving
proton (4) and electron (5) transfer give rise to lines, e.g. pε=a× pH + b
(where a∧b are constants), with slope=a.[2]
(ii) Complete the 1st and 3rd column of the table below on redox equilibria
relationships mentioned in (i) and (ii) above for a mark per completed cell
[6].

Species transferred Type of line Relationship for line

Electron Horizontal pε=b
Proton Vertical pH = C
Proton and electron Sloped line pε=apH + b

QUESTION TWO (Freshwater) [35 Marks]

(a) When generating an environmentally representative pε versus pH diagram what

tool do you use and give two examples of parameters of interest. [4]
ANSWER: Geochemical computer models.
PHREEQC and ORCHESTRA

(b) What are diatoms [2] and what does one infer from diatom records [2]
• ANSWER: Diatoms are algae with silicified cell walls.
Diatom record in dated sediments rules out long-term acidification processes as
the cause of the dramatic change in pH.

(c) Complete the 2nd column of the table below that deals with acidification from
Aluminium [5].

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 Monomeric Al ion Predominating pH
3 +¿¿
Al pH < 3
2+¿¿
Al(OH ) 4.5 – 6.5
+¿¿
Al(OH )2 4.5 -6.5
Al(OH )3 4.5 – 7.5
−¿¿
Al(OH )4 pH > 7

(d) In the European Community (EC), a standard concentration use for Aluminium
is called the MAC. Explain the term and give is value. [4]
ANSWER:
(i) In EC, a standard environmental concentration termed the MAC means
the
Maximum Admissible Concentration
(ii) The MAC for aluminium is 200 μg/L
(e) One of the major pollution problems affecting freshwaters that is of acid waters
discharged from coal and metal mines. [18]
(i) What is this problem called? [1] and what is its abbreviation? [1]
ANSWER:
This is called Acid Mine Drainage
and its abbreviation is AMD
(ii) What substance leads to problem? (formula, chemical name and colloquial
name) [3]
ANSWER:
The substance that leads to this problem is Iron(ii) sulfide
Its chemical formula Is (FeS2)
its colloquial name is Pyrite
(iii) Give chemical reaction equation that leads this problem [2]
ANSWER: 2FeS2(s) + 2H2O +7O2(g) → 2FeSO4(s) + 2H2SO4(1)

(iv) Name two chemical species that are brought in solution by the reaction.
[2] ANSWER:
The two chemical species brought into solution are sulphuric acid and
iron sulphates [2]
(v) The above reaction releases Fe2 +¿¿. Write two addition reactions catalysed
by bacteria that utilize ferrous ion in its further oxidation of ion. [4]
ANSWER:
1st Rxn is: 4Fe2+ + O2(g) + 4H+ ⇌ 4Fe3+ + 2H2O
¿+
2−¿ +16 H ¿
2+¿+ 2 SO4 ¿
3 +¿+8 H 2 O ⇌ 15 Fe
2nd Rxn is: FeS2 ( s ) +14 Fe

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(vi) What are the iron compounds this oxidation are generally termed iron
(hydr)oxides [1] Give two names of examples of these compounds and
their formulae [4]
ANSWER:
Examples are ferrihydrite & goethite [1]
Formulae are (Fe(OH)3) and (FeOOH) [4]

THE END

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