Applied Water Chemistry Updated 2009-06-17

Department of chemical engineering

Technical University of Lund

Lab 2: The CO2/H2O system

Supervisors:
1. Introduction
Through the circulation of carbon on the earth, carbon dioxide becomes a natural component in the
atmosphere. It is also stored in large quantities in the oceans and in the terrestrial systems. Between
these systems there is always an exchange of molecules.

Normally there was about 0.03 vol% CO2 in the atmosphere. Human emissions have, since the
beginning of the industrial revolution, increased the CO2 content by approximately 30%. Due to the
constant exchange between water and air, the emissions have not only affected the atmosphere, but
also the aquatic systems. The solubility of carbon dioxide in water depends on the partial pressure
of the gas in the atmosphere.

The objective of this laboratory is to gain understanding of the mechanisms that affect the
CO2/H2O-system. During the exersice you will gain understanding of how changes in CO2 content
in the atmosphere influence the pH in aquatic systems. You will also use equilibrium expressions
and Henry's law to determine an equilibrium graph for the system.

2. Theory
The partial pressure of CO2 in the atmosphere is currently around 3.8·10-4 atm. In rainwater the
amount of dissolved CO2 corresponds to the equilibrium between gas phase and liquid phase. In
soil-, surface- and groundwater levels are normally significantly higher than the corresponding
amount in a system at equilibrium with the atmosphere. The CO2 in the air dissolves in water
according to a series of equilibrium equations. These can be simplified to:

CO 2 (g) + H2 O ⇔ H2 CO 3 (aq) -logK H (20o C ) = 1.399 (1)

H2 CO3 (aq) ⇔ H+ + HCO3- pK a (20o C) = 6.398 (2)

HCO3- ⇔ H+ + CO 32- pK a (20o C ) = 10.359 (3)

auto proteolysis of water

H2 O ⇔ H+ + OH− pK W (20o C ) = 14.173 (4)

In slightly acidic (pH~6) solutions (2.2) is dominating.

2.1 Henrys Law

The solubility of a gas in liquid is strongly influenced by the pressure over the liquid. According to
Henry's law the solubility of a gas in a liquid is directly proportional to the partial pressure of the
gas.

[H2 CO3 (aq) ] = K H ⋅ PCO2 (5)

where the solubility has the unit mol/l, Henry's constant, KH (kmol m-3 atm-1) is specific for each
gas and temperature and P is the partial pressure (atm) of the gas above the solution. Reaction (1)
above can be described using Henry's law.
2.2 Equilibrium graph
In a standard acid-base titration an acid (or base) is added to a known solution of a base (or acid)
and the sequence is measured by a pH meter. A pH-titration curve is obtained by plotting the pH of
the solution versus the volume of added acid (or base).(Chang Chapter. 17.3, pp. 544)
In this laboratory lesson, a gas mixture of N2 and CO2 is bubbled through water in order to allow
CO2 to dissolve in water, and affect the pH. An equilibrium between gas and water will be reached.
Several measurements will be made, using mixtures ranging from 0.1-5% in CO2 content. An
equilibrium curve which demonstrates CO2 content versus pH can then be plotted.

3. Apparatus

3.1 List of lab equipment

pH-meter
magnetic stirrer and magnet
250 ml beaker
plastic hose
metal clamp
stand

3.2 Chemicals
Deionised water
NaCl
N2 gas with 0.1%, 0.3%, 1%, 5% CO2 content
Buffer solutions for calibration

4. Execution
1. Calibrate the pH-meter as directed
2. Fill a 250 ml beaker with distilled water to 2/3. Add 0.1 g NaCl.
3. Set up the equipment as shown in the figure above.
4. Open the N2/CO2-tube to barely noticeable flow and connect it to the beaker. Adjust the gas
flow until a steady stream of bubbles through the water is obtained.
5. Start the magnetic stirrer and set to the vigorous stirring. Let the system stabilise. (around 5
minutes) Note the pH, change gas, and repeat the experiment.
Go from a gas with low CO2 content to a gas with high CO2 content.

The gas tanks are opened by turning the tap on top of the tube. Open the tap fully and then turn
back half a turn. The first gauge makes a deflection, while the other shows zero. Open the tap under
the pressure gauge by turning it inwards. The second pressure gauge gives response. The gas tanks
are closed by first closing the tap on top. Let the governor and the hose empty. When the pressure
gauge shows zero, turn off the tap under pressure gauges by turning it outwards.

5. Calculations and evaluation

With the help of your measurements (at least 8 points, collect values from the other groups) you
will determine KH. This is done by linearization of the equations that describe how pH varies as a
function of carbon dioxide pressure. When you have linearized the equations you will see that KH
can be obtained by linear regression. The “small quadrate method” can be made in Excel, with the
Matlab function POLYFIT, or by hand.

But first, find an expression for pH as a function of PCO2 if:

⎡⎣H+ ⎤⎦ ⎡HCO − ⎤
K = ⎣ 3 ⎦
= 10 −6.4 (6)
H2CO3
[H2 CO3 ]
Tip: Which parameters do you have and which of the equations (1) - (6) you can use? What ions are
present in the solution? Which can be neglected? (The solution will be slightly acidic)? Remember
that a solution must be in charge balance.

Compute the all values of KH, which are produced in your lab group. How much do the
measurements vary? Is the variation systematic?

Issues:
What happens in lakes and seas where the CO2 pressure increases?
How are the ecosystems affected?
How much CO2 can the oceans dissolve when the partial pressure of CO2 increases in the
atmosphere?
Do the obtained results correspond with the theory? If not, why?

5.1 Lab Report

Lab report must include:
• A brief description of the labs and its purpose. Why is the CO2/H2O-system important?
• Derivation of pH = f (PCO2)
• Your raw data in appendix
• Diagram illustrating how you used the “small quadrate method” to derive KH
• Chart with the complete model (pH vs. PCO2) from measurement data.
• Conclusion