Unit 4.

Heterogenous systems

Class notes

1. Gas-liquid equibria – Open systems

Dissolved oxygen and hypoxic dead zone
Global carbon cycle, climate change, ocean acidification
Groundwater sampling
Aeration – wastewater treatment
Gas concentrations

• Ideal gas law

PV
i = ni RT
ni Pi
[i ] = =
V RT

– Pi is the partial pressure of compound i

• Expressed using mole fraction of compound i (xi) and total pressure (Ptotal)

Pi = xi Ptotal
Gas concentrations

• What is the concentration of oxygen in air?

Gas-liquid equilibria
Often represented by the “reaction”:

A(aq) = A(g)

Equilibrium constant: Henry’s Law

[ A( g )]
H=
[ A(aq)]

• Can be dimensionless but typically different units are used for gas
concentrations and aqueous concentrations
Henry’s law
A(aq) = A(g)

Henry’s Law often expressed as:

PA
H=
[ A(aq)]
• partial pressure of A in units of bar (SI)
• dimensions of bar L mol-1
• 1 bar = 105 Pa = 0.9869 atm
Henry’s constant for water
PA
H=
[ A(aq)]

H, 20°C
– depends on strength of bond with water Species (bar L mol-1)
• mainly electrostatic N2 1560
– ions: H ~ 0 O2 790
• strong electrostatic bonds with water
– polar compounds: low H CO2 30.2
• electrostatic bonds with polar water H2S 9.8
– non-polar: high H NH3 0.017
• weak bonds with water
Henry’s law example

• What is the concentration of oxygen in dilute water at 20C at sea level?

Henry’s law constant
• Temperature effect
– H increases with temperature PA
• greater freedom in gas phase
H=
[ A(aq)]
• lower solubility of O2 in aqueous phase

What does this mean for rising temperatures and CO2(g) concentrations?
Gas liquid equilibria
• H increases with ionic strength
• for example, chloride concentration
• “salting out” resulting in less O2 in salt water
• mechanism
– salt reduces water available for solvation
– water cannot interact with (hydrate) gas solute
Gas liquid equilibria

• What is the concentration of oxygen in seawater (19.3 g Cl- kg-1) at 25C?

chloride concentration (g kg-1)

Gas liquid equilibria
• Interpret this data: CO2 concentration in the atmosphere.
Gas liquid equilibria
• What is the concentration of CO2 in surface water in equilibrium with the
atmosphere? H =30.2 bar L mol-1

– PCO2 = 356 matm= 10-3.46 bar

Carbonate equilibria (open system)
• Carbon dioxide in water

CO2(g) = CO2(aq) (slow)

CO2(aq) + H2O = H2CO3 (very fast)

CO2(g) + H2O = H2CO3

CO2(aq) = H2CO3

H2CO3*
Carbonate equilibria (open system)

CO2(g) + H2O = H2CO3* H-1 = (30.2 bar L mol-1)-1 = 10-1.48

H2CO3* = H+ + HCO3- Ka1 = 10-6.33

HCO3- = H+ + CO32- Ka2 = 10-10.33

PCO2 ~ 3.5x10-4 bar = 10-3.46 bar in the atmosphere

 Carbonate equilibria (open system)
• What is the pH of pure water in equilibrium with carbon dioxide in the
atmosphere?
Carbonate equilibria (open system)

-2

-4

-6 [H+]
[OH-]
log C

[H2CO3]
-8 [HCO3 -] Total
[CO3 -2]
[H2CO3]o
concentration
CT
of carbonates
-10
in system

-12

-14
0 2 4 6 8 10 12 14
pH