Chapter 1.

Chemical Concept
1. Terminology
2. Concentration Units
3. Hydrogen Ion Concentration
4. Chemical Equilibria
5. pH and Alkalinity
6. Chemical Kinetics
7. Gas Laws
8. Colloidal Dispersions

2020 Physicochemical Water Treatment Engineering

1. Terminology
- Valence

- Radicals

 Certain groupings of atoms act together as a unit. OH-, HCO3-, PO43-.

 More generally, radicals mean atom, molecule, or ion that has

unpaired valance electrons.

SO4•-

OH•

- Equivalents (당량); Normality

- Equivalent weight (EW): a mass of one equivalent, 당량, 그람당량)

EW = MW (분자량)/Z

Z = (1) Absolute of value of the ion charge

(2) Number of H+ or OH- ions a species can react with or yield in an acid-base
reaction
(3) Absolute value of the change in valence occurring in an oxidation-
reduction reaction.

CaCO3 + 2H+ = Ca2+ + H2CO3

EW = 100g per mole/2 = 50g per equivalent; as CaCO3

Let’s think about the cases below.

Fe(0)  Fe2+ + 2e-

Fe(0)  Fe3+ + 3e-

2. Concentration Units

1) Common expression

- For solution, mg/L commonly

 Assuming density of water to be 1000 kg/m3,

mg/L becomes mg/kg  g/106g  ppm (parts per million)

 It is better to use mass or volume unit specifically (like mg/L,

mg/kg) rather using ppm.

 1%: parts per cent; 104 ppm

- For soil, mg/kg, for air, L/L

2) meq/L

1 eq/L = 1N

CaCO3 100 mg/L to meq/L?

 50g CaCO3/eq  50 mg/meq

(100 mg CaCO3/L)(meq/50 mg CaCO3) = 2 meq/L

3) as CaCO3

- Used for alkalinity, hardness, etc.

2 meq HCO3-/L as CaCO3 ?

(2 meq HCO3-/L)(50 mg CaCO3/meq HCO3-) = 100 mg/L as CaCO3

1 meq/L Ca+2 + 3 meq/L Mg+2 = Hardness of 4 meq/L

=> 4* 50 mg/L as CaCO3

 Can express hardness (from two chemicals) as a single term

3. Hydrogen Ion Concentration

pH = -log [H+] Precisely, pH = -log{H+}

{ } represents activity

- Need of pH adjustment: Numerous reactions are affected by pH

 Solubility: Al(OH)3 precipitation

 Carbonate species distribution (pC-pH diagram)

 Enzyme activity (activate sludge)

- May be the single most important parameter in Environmental Eng.

4. Chemical Equilibria
- Chemical equilibrium: the state in which the chemical activities or
concentrations of the reactants and products have no net changes over time.
1) Kinetics vs. Equilibrium

- Kinetics: Study of speed of reaction “Rate”

Not important for very fast reactions such as neutralization

- Equilibrium
 Defines the condition after reaction has progressed to the
maximum extent.
 Gives information on the final expected chemical composition.
 Examples of equilibrium expressions: K, G, H

2) Equilibrium constant

aA + bB cC + dD

At equilibrium, r1 = r2, “Equilibrium constant”

- Equilibrium constant describing solid dissolution: Ksp (Solubility Product)

CaCO3(s) = Ca2+ + CO32-

Ksp = [Ca][CO32-] = KsK (Conc. of solid is treated as a constant)

 - Van’t Hoff approximation for temperature

KT 2 H o T1 T2
ln   ( )
KT 1 R T1T2

5. pH and Alkalinity

1) Alkalinity
- Definition: Capacity of water to neutralize H+
- Source

CO2(g) = CO2(aq) atmospheric CO2 dissolution into water

CO2(aq) + H2O = H2CO3 [CO2(aq) + H2CO3] = [H2CO3*]

difficult to distinguish between and CO2(aq) and H2CO3

=> introduce an hypothetical species
H2CO3* = H+ + HCO3- pKa = 6.4 (CO2 hydration and H2CO3 dissociation rxn combined)

HCO3- = H+ + CO32- pKa = 10.3

H 2O = H+ + OH-

- Analytical definition
Alkalinity = [HCO3-] + 2[CO32-] + [OH-] - [H+]
=> unit: meq/L or mg/L as CaCO3
1 mol = 1 eq for HCO3-
[OH-] and [H+] negligible at neutral pH conditions
- Measurement: titration using 0.02N H2SO4

- Alkalinity addition: Na2CO3 (soda ash), CaCO3, CO2 supply, Ca(OH)2

2) Buffer

- Substances that offer resistance to a pH change

HCO3- + OH- = CO32- + H2O

HCO3- + H+ = H2CO3

- The above reactions show the importance of alkalinity with respect to

pH buffering. Alkalinity addition to treatment systems is sometimes
required.

6. Chemical Kinetics

- Case for a single reactant conversion (irreversible; common for

contaminants removal). Simple but very useful case.

AB ; C = conc. of A

dC/dt = - kCn : general expression for nth reaction order

: change in concentration of A over time is

proportional to Cn

1) Zero-Order Reaction
𝑑𝐶
𝑘
𝑑𝑡
- Concentration changes over time regardless of concentration of A.
 Integration gives 𝐶 𝐶 𝑘𝑡 When C=C0 at t = 0

Fitting concentration vs. time curve gives a straight line to obtain k.

2) First-Order Reaction

dC
 kC C  C 0e  kt
dt

- “Exponential decay”
- Most frequently observed kinetics in environmental eng.
- BOD reaction and many biological processes follow this law.

- Linearizing the eq. gives lnC = lnC0 – kt

- Fitting log (concentration) vs. time curve gives a straight line to

obtain k.
 3) Second-Order Reaction

dC 1 1
 kC 2   kt
dt C C0
1
C  C0
1  kC 0t

- Fitting 1/concentration vs. time curve gives a straight line to

obtain k.

Comparison

- Curvature: 2nd > 1st > Zero

Data analysis
i. Plot the data using linearized forms of the rate equations. Like (ln C vs.
time plot)
ii. Fit the data using Excel or linear regression feature of the calculator
iii. Check for the linearity using the R2 (correlation coefficient) value
 “Specify unit always”

- Need to learn how to conduct this analysis using your calculator.

Temperature effects

- Arrhenius equation based on “Ea (activation energy)”

(T2 T1)
k 2  k 1

 The larger the , the stronger is the temperature dependence.

 1.047 for BOD (Phelps, 1944) widely used but does not apply at
cold temp.

 Rule of thumb: Rate doubles for a temperature rise of 10 C

7. Gas Laws

1) Ideal gas law

PV = nRT ; a relationship between the pressure, volume,

temperature and no. of moles of a gas at low density

2) General gas law

P1V1 P2V 2

T1 T2

3) Henry’s law

- Gas-liquid equilibrium for dilute solution

 Cs = (Constant) Pg
Cs = liquid phase conc.
Pg = Partial pressure of the gas above the liquid

Pg = HX ; another form

H = Henry’s law constant

X = Mole fraction of solute

Pg = HCl ; more common form

Cl = liquid phase conc.(mg/L)

H = Henry’s law constant (atm∙L/mg)

Need to be careful about the unit of ‘H’

8. Colloidal dispersions

1. Size and types of colloids

- Size between dissolved solids and suspended solids (1 nm  1 m)

- Many suspended materials in WTP and WWTP are colloids

- Solids such as clay, organic debris; liquid such as oils secreted by algae or
oils present in wastewaters.

2. Properties

- Surface area/mass ratio is very high

 1 cm3 of 10 nm colloids => surface area of 600 m2

 Thus surface phenomena predominate and control the behavior of

colloidal dispersions

 Examples of surface phenomena: adsorption, surface catalysis.