More about Henrys Law

Introduction
Concentration of gas in solution = constant partial pressure of gas

This appendix gives more information about calculations involving Henrys Law. Henrys Law may be expressed in words as: The mathematical expression is:
c = KH p

Henrys Law can be visualized simply by imagining a gas (mixed with air) above a liquid in a closed container (see Fig A11.1).

Fig. A11.1 The molecules of dissolving gas are shown in red. According to Henrys Law, as the partial pressure of the dissolving gas doubles, the concentration of dissolved gas also doubles.

Henrys Law says that if the partial pressure of the gas doubles, the equilibrium concentration of the dissolved gas also doubles. The proportionality constant is Henrys Law constant, KH, which depends upon the gas involved and on the temperature of the solution. One of the most important cases to which Henrys Law is applied is the dissolution of oxygen in water. Fish depend on dissolved oxygen to breathe. At 25C, KH (O2 in H2O) = 1.28 103 mol dm3 atm1. The following example shows how to calculate the concentration of oxygen in water. This involves applying Henrys Law, but there is a minor adjustment because the water vapour contributes to the total air pressure around us.

APPENDIX

11

APPENDIX 11

Example 1
A beaker of water lies in a room at 25 C. The total gas pressure inside the room is 101.325 kPa (1 atm). What is the concentration of oxygen gas in the water in (i) mol dm3 (ii) mg dm3? (Assume that air contains 20.9% oxygen by volume. The equilibrium vapour pressure of water at 25 C is 3.17 kPa.)

Answer
In this example we calculate: The air pressure sitting on the water. The partial pressure of oxygen sitting on the water. Finally, the concentration of dissolved oxygen using Henrys Law. The beaker is not sealed, but as an approximation we will assume that the water vapour pressure above the beaker is the equilibrium vapour pressure of water at 25 C, i.e. 3.17 kPa. The pressure of air on the liquid water is (total gas pressure) (water vapour pressure) 101.325 3.17 98.16 kPa The pressure of oxygen is 20.9% of this, i.e. (20.9/100) 98.6 20.6 kPa. We now have to change the pressure to atmospheres. Since 101.325 kPa 1.000 atm, 20.6 kPa is (20.6/101.325) 1.00 0.203 atm Applying Henrys law (KH(O2) 1.28 103 mol dm3 atm1), c(O2) KH p(O2) 1.28 103 0.203 2.60 104 mol dm3 To convert this to mg dm3, we multiply by the factor: molar mass of oxygen 1000 Since M(O2) 32 g mol1 c(O2) 2.60 104 32 000 8.3 mg dm3 O2 This is the observed value (Fig. 11.6, book p. 185).

Exercise 11A
Henrys law
(i) Show that if we ignore the contribution of the water vapour pressure in Example 1, that the calculated dissolved oxygen concentration is 8.6 mg dm3. (ii) The partial pressure of CO2 gas in air is 3.5 104 atm at sea level. Estimate the concentration of carbon dioxide (mg dm3) in water in equilibrium with air at 25 C. (iii) Estimate the equilibrium concentration of nitrogen (from the air) in water at an air pressure of 1 atm and a temperature of 25 C (the percentage of N2 by volume in air is 78.05%).

MORE ABOUT HENRYS LAW

Exercise 11B
Use of Henrys law to estimate the oxygen dissolved in a lake
The air pressure on top of a mountain is 86.7 kPa (0.855 atm). The temperature was 15 C. Estimate the concentration of oxygen (in mg dm3) in a lake at the top of the mountain (KH(O2) 1.57 103 mol dm3 atm1 at 15 C).

Revision questions
1. (i) Above 0.001 atm pressure, hydrogen chloride does not

follow Henrys law using water as solvent, but the law is still followed using benzene as solvent. Explain this.
(ii) A zzy drinks dispenser operates using pure CO2 at a

pressure of 2.0 atm. Calculate the concentration of carbon dioxide gas dissolved in water in equilibrium with air at 25 C.

2. A sealed ask is half-lled water. The gas above the water consists of 0.10 atm methane (CH4) and 0.10 atm hydrogen (H2). Calculate the concentration of methane and hydrogen in the water in mg dm3. [T = 25C. KH values listed in Table 11.6 on page 184 in the book].

Answers
Exercise 11A
(i) The total gas pressure is 101.325 kPa. The pressure of O2 is (20.9/100) 101.325 21.2 kPa (0.209 atm). c(O2 ) 1.28 103 0.209 2.68 104 mol dm3 32 1000 2.68 104 mg dm3 8.6 mg dm3 (ii) c(CO2) KH 3.5 104 3.38 102 3.5 104 1.2 105 mol dm3 0.52 mg dm3 (iii) Ignoring the vapour pressure of water, the pressure of nitrogen is (78.05/100) 101.325 79.08 kPa or 0.781 atm c(N2) KH 0.781 6.48 104 0.781 5.06 104 mol dm3 14.2 mg dm3

Answers to revision questions

1. (i) HCl(g) remains as unionised HCl molecules in a non-polar solvent. Deviations from Henrys law are more likely to occur when the solute chemically reacts with the solvent. (ii) c(CO2) KH 2.0 3.38 102 2.0 6.8 102 mol dm3 (This is about 3 g dm3.) 2. The concentration of gas in water, c, at equilibrium is equal to KH p, where p is the pressure of the dissolving gas. Where there is a mixture of gases, Daltons Law is assumed to apply at low partial pressures, and so the gases are treated separately. For methane: conc of dissolved methane = 1.34 103 0.10 = 1.34 104 mol dm3. Since m(CH4) = 16 u c = 1.34 104 16 1000 = 2.1 mg dm3 (ppm). For hydrogen, c = 7.90 104 0.10 = 7.90 105 mol dm3. Since m(H2) = 2 u c = 7.90 105 2 1000 = 0.16 mg dm3 (ppm).

Exercise 11B
p(O2) (20.9/100) 0.855 0.179 atm c(O2) KH 0.179 1.57 103 0.179 2.81 104 mol dm3, or 9.0 mg dm3. (Although the partial pressure of O2 is lower than at sea level, the lower temperature ensures a higher oxygen gas concentration than observed at sea level at 25C.)

Rob Lewis and Wynne Evans, 2001, Chemistry, Palgrave.