II.

Process Fundamentals

Environmental Remediation 2020

A. A Little Chemistry
1. Nomenclature and Structure
1) Aliphatics

systematic vs. common name

2) Aromatics

3) Polynuclear Aromatic Hydrocarbons (PAHs)

- Also Polycyclic Aromatic Hydrocarbons: Groups of aromatic rings
containing only carbon and hydrogen

4) Functional Groups

Ester Ketone

Amines
2. Organics Classification Based on Volatility
- No distinct lines can be drawn between volatiles and nonvolatiles
- Important when considering risk of a chemical

1) Volatile organics
- Low molecular weight, high vapor pressure, high Henry’s constant,
low organic carbon partition coefficient (Koc)
- Example: Numerous solvents
- Soil Vapor Extraction (SVE) and thermal desorption can be applied to
treating volatiles

2) Semivolatile organics
- A subgroup of VOCs that tend to have a higher molecular weight
and higher boiling point temperature.
- Examples:
phenol 3-nitroaniline
2-chlorophenol 2,4-dinitrophenol
1,2-dichlorobenzene diethyl phthalate
hexachloroethane pentachlorophenol
nitrobenzene hexachlorobenzene

3) Nonvolatile organics
- Little to no volatility even at elevated temperatures

3. Pesticides and Herbicides

- Chemical compounds used to control insects, rodents, parasites, fungi,
and undesirable plants
- Organic pesticides (Table 3-2): chlorinated vs. organophosphate
- 8 of 12 initially designated POPs (Persistent Organic Pollutants)
(Stockholm convention, 1995)
4. Polychlorinated Biphenyls & Dioxins
- PCBs: Used in electrical transformers and capacitors; 210 congeners
- PCDD/Fs

5. EDCs (Endocrine Disrupting Chemicals) and PPCP

(Pharmaceuticals and Personal Care Products)

- EDCs
 Numerous estrogenic materials
 Behaves similar to estrogenic hormones or blocks them.
 Bisphenol A, dioxins
- PPCP: antibiotics, growth hormones, shampoo, etc.
B. Physical-Chemical Properties
- Properties for 250 selected chemicals in Appendix B
- Interested in distribution among three phases (gas, soil, water)

1. Solubility (Water solubility)

- Solubility of chemicals in water is a function of temperature and the
particular chemical species
- Ksp
an example of Ksp expression: [Me2+][OH-]2

- Significance
 A simple indicator of mobility (mobile vs. immobile)
 important in terms of transport &
treatment (solubilization in soil washing, etc.)
 Heavy metals example
 solubility vs. pH
 soil washing: acid addition
 stabilization: lime addition
 Hydrophobic chemicals such as PAHs have very low solubilities
Solubility of a metal

S C , free metal aq 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑚𝑒𝑡𝑎𝑙 𝑐𝑜𝑚𝑝𝑙𝑒𝑥𝑒𝑠

𝐶 , 𝑃𝑏 𝑃𝑏𝐶𝑙 𝑃𝑏𝐶𝑙 𝑃𝑏𝐶𝑙 𝑃𝑏𝐶𝑙

CT,CO3 = 10–3 M

2. Vapor pressure
- Vapor pressure of a pure liquid is the pressure exerted by the
vapor on the liquid at equilibrium in a closed system

- Raoult’s law
 Gas-liquid equilibrium for a pure liquid
 Describes the equilibrium partial pressure of a volatile
organic in the atmosphere above an ideal solvent
 p a  pvp ,a X a : Raoult' s law
p a  partial pressure of componet a over the solution Non-Aqueous Phase Liquids
pvp ,a  vapor pressure of pure component a
X a  mole fraction of component a in solution

- Study Example 3-4

3. Henry’s constant
- Special form of Raoult’s law in dilute aqueous solutions
- Gas – liquid equilibrium. Example?
- Suitable for dilute systems
Ex. Volatilization of solutes dissolved in water
- Concentration in gas  concentration in liquid

𝑷 𝑯𝑿

𝑃 𝐻𝑋

𝑝 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑛 𝑔𝑎𝑠 𝑎𝑡𝑚

𝑚𝑜𝑙𝑒𝑠 𝑖
𝑋 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑚𝑜𝑙𝑒𝑠 𝐻2𝑂
𝑎𝑡𝑚
𝐻 𝐻𝑒𝑛𝑟𝑦 𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛

Introducing liquid phase concentration gives

𝑃 𝐻 𝐶

𝐶 𝑋𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛

𝑚𝑜𝑙𝑒𝑠 𝑖 𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠
𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑙 𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑐. 𝑜𝑓 𝐻2𝑂

𝐶 𝑋 𝐶 Substitute this into the above gives

𝑃 𝐻 𝑋 𝐶 𝐻𝑋 𝐻
𝐻
𝐶
𝐻
𝑃 𝐶
𝐶
 𝐶 𝐻 𝐶

𝐻 dimensionless Henry s constant

𝑃𝑉 𝑛𝑅𝑇
𝑛
𝑃 𝑅𝑇 𝐶 𝑅𝑇 𝑃 𝐻 𝐶
𝑉
𝐶 𝑅𝑇 𝐻 𝐶

𝐻
𝐶 𝐶
𝑅𝑇
𝐻
𝐻
𝑅𝑇

4. Diffusion coefficient
1) Advection (이송; 이류; 대류=convection)

- Bulk movement of fluids and constituents between locations

- Surface water: from a high to a low point
- Groundwater: from a point with a high head to a point with a low head

∂C ∂C ∂2C
𝑢 𝐷 2 𝑅
∂t ∂x ∂x

“Advection – Diffusion - (Reaction) Equation”

2) Diffusive transport (Collectively “diffusion” in many books)

- Seemingly random mixing processes within fluids

- Movement of a contaminant under the influence of a concentration
gradient
 a. Fick’s first law

dC dC
𝐽 ∝ 𝐽 𝐷
dx dx

J: flux [M/L2/T)]
D: diffusion coefficient (L2/T)
(-) sign :

b. Three Mechanisms
i. Molecular diffusion
- Random motion of chemical molecules  Brownian motion
 vibrational, rotational, translational motion

ii. Turbulent diffusion

- due to microscale turbulence or eddies
- random and chaotic time dependent motions
(wiki)

iii. Dispersion
- due to tortuous path through porous media (GW) =>
results in velocities different from those predicted by Darcy’s law

- velocity gradient caused by shear forces (surface water) =>

results in the mixing along the direction of flow

- Which diffusion mechanism is predominant in GW?