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Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

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Page 1: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

Gas-Solution ProcessesGas SolubilityRaoult’s Law

Edward A. Mottel

Department of Chemistry

Rose-Hulman Institute of Technology

Page 2: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Solutions

Reading assignment: Fine, Beall & Stuehr: Chapter 9.1, 9.3

A homogeneous mixture of two or more substances in a single phase.• Solute

· The material dissolved in a solution.• Solvent

· The medium into which a solute is dissolved to form a solution.

Page 3: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Solutions

What is the solute and what is the solvent?• An ounce of isopropanol (rubbing alcohol)

is added to a cup of water.• A drop of water is added to a cup of

isopropanol.• A cup of water is added to a cup of

isopropanol.

Page 4: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

MolalityOne cup of isopropanol is mixed with one cup of water.

isopropanol

CH3-CHOH-CH3

0.78 gmL-1

water

1.00 gmL-1

Molality (m) = moles of solute per kilogram of solvent

What is the molality of the solution?

Page 5: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Henry’s Law

Assumes thatthe gas and the solventdon’t react with each other.

mdissolved gas = k · Pgas

Page 6: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Henry’s Law

mdissolved gas = k · Pgas

dissolved gas = k’ · Pgas

The concentration of the gas in solutioncould also be defined in terms ofmole fraction of gas in solution.

Page 7: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Henry’s Law

Partial Pressure of Gas (torr)0

0mo

les

of

dis

solv

ed g

asp

er k

ilo

gra

m o

f s

olv

ent

(m)

slope = Henry’s Law constant (k)

Page 8: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Solubility of Gases in Water1 atm gas pressure above solution

CH4

O2

CO

N2

He

Temperature (ºC)

Sol

ubili

ty

(mm

ol/k

g so

lven

t)

00

1

2

10 20 30

What effect does heating have onthe amount of dissolved gas?

Page 9: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Solubility of Gases

The solubility of gas in liquids usually decreases with increasing temperature.

However, some gases become more soluble in organic solvents with increasing temperature.

Page 10: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Carbonated Beverages

mdissolved CO2 = 0.034 m·atm-1 · PCO2

Packaged under about2 atm of CO2 pressure.

Why does acarbonated beverage

go "flat" overnight?

Page 11: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Diver's Bends

Caused by dissolved nitrogen in the blood.• A diver can go deep for a short period of

time, if nitrogen gas does not have a chance to equilibrate in the blood.

• How do the partial pressures of nitrogen and oxygen in the blood compare at 1 atm pressure and under 33 feet of water?

Page 12: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Physiological ImplicationsHenry’s Law

What are the problems associated with breathing pure oxygen for a sustained period?• How do scuba divers avoid breathing high

partial pressures of oxygen? Why is it harder to work and breathe in the

mountains?• Why do athletes train in the mountains?

Page 13: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

Gas-Solution ProcessesColligative Properties

Edward A. Mottel

Department of Chemistry

Rose-Hulman Institute of Technology

Page 14: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Temp (°C) P (torr)10 9.220 17.530 31.840 55.350 92.5

Vapor PressureWater

On the graph where is the boiling point located?

What does a vapor pressure of water graph look like?

Page 15: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

Vapor Pressure of Water

0

20

40

60

80

100

0 10 20 30 40 50

Temperature (°C)

Pre

ssur

e (t

orr)

What will be the vapor pressure whenthe temperature is 100 °C?

Page 16: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Vapor Pressure of Water

Which of thedozen water moleculesshown are evaporating?

What factorsdetermine whether

a molecule will evaporate?

Page 17: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Which Is More Volatile?Water or Isopropanol

Vapor Pressure of Water & Isopropanol

0

40

80

120

160

0 10 20 30 40 50

Temperature (°C)

Pre

ssur

e (t

orr)

WaterIsopropanol

Page 18: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Vapor Pressure of a Solution

What factorsdetermine the totalvapor pressure of the solution?

Page 19: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Raoult’s Law

The vapor pressure of an ideal solution is equal to the sum of the vapor pressure of each component times its mole fraction.

AP BP totalP A B

Page 20: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

P°A is thevapor pressureof pure A.

AP BP totalP A B

If the solventor solute is non-volatile,

then P° for that species is zero.

Page 21: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Non-ideal solutions have vapor pressures higher or lower than predicted.

AP BP totalP A B

Raoult’s Law

Page 22: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Raoult’s Law Application

Distillation: The separation of one component from a solution by boiling and condensation of the vapor.

Page 23: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Benzene-Toluene Distillation

One mole of benzene is mixed with three moles of toluene.

What will be the vapor pressure of the solution at 88 C.

• Benzene (C6H6) and toluene (C6H5CH3) form an ideal solution.

• Pbenzene is 960 torr at 88 C

• Ptoluene is 380 torr at 88 C

What other questions could be asked?

Page 24: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Benzene-Toluene Distillation

One mole of benzene is mixed with three moles of toluene.

What will be the composition of the vapor that is condensed?

Microsoft Excel Worksheet

Page 25: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Distillation

Distillation separates one compound from another because the vapor and the solution have different compositions.

How could you make a solution containing two volatile components very pure?

Page 26: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Fractional Distillation

Page 27: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Not All Compounds can beSeparated by Distillation

Non-ideal solutions that have the same composition in solution and the vapor are called azeotropes.• Isopropanol (BP 82 C) and water

(BP 100 C) forms a 80.4 C azeotrope of composition isopropanol = 0.878, water = 0.122

Page 28: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Colligative Properties

A physical property of a solution which depends upon the concentration of the solute, but not its nature or identity.

Examples:• Vapor pressure lowering• Boiling point elevation

Page 29: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Vapor Pressure Lowering

Why does the dissolution of a non-volatile soluteresult in a lower solution vapor pressure

than the pure solvent?

Describe the cause based on a mathematical argumentand a mechanical argument.

Page 30: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Under what conditions does boiling occur?

Temperature (oC)

0

200

400

600

800

0 20 40 60 80 100 120

Vapor Pressure ofWater Solutions

Pre

ssu

re (

torr

)

WaterSugar Water

Page 31: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Temperature (oC)

0

200

400

600

800

0 20 40 60 80 100 120

Vapor Pressure ofWater Solutions

Pre

ssu

re (

torr

)

WaterSugar Water

What is the vapor pressure of a 0.10 mole fraction sugar in water solution at 100 °C?

Page 32: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Temperature (oC)

0

200

400

600

800

0 20 40 60 80 100 120

Vapor Pressure ofWater Solutions

Pre

ssu

re (

torr

)

WaterSugar Water

If the vapor pressure of a solution is lowered, why is the boiling point elevated?

Page 33: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Boiling Point Elevation

T is the increase in boiling point kb is the boiling point (ebullioscopic) constant

· kb = 0.512 Km-1 for water m is the molality of the solution

T k m ib

Page 34: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Boiling Point Elevation

Sugar water does not conduct electricity. kb = 0.512 Km-1 for water What is the boiling point of 0.10 mole fraction

sugar water solution?

T k m ib

Page 35: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Boiling Point Elevation

i is the multiplicative factor to account for ions

• if a compound does not ionize then there is one particle per molecule and i = 1.

• if a compound breaks into two ions then i = 2, etc.

T k m ib

Page 36: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Rank the following solutions in terms of increasing boiling point

• water• 0.2 m salt water• 0.3 m sugar water

T k m ib

Page 37: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Freezing Point Depression

The dissolution of a solute in a solvent results in a lower freezing point for the solution.

T k m if

Page 38: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Freezing Point Depression

How does an impurity changethe freezing point of the triangular molecules?

Page 39: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Freezing Point Depression

T is the decrease in freezing point kf is the freezing point (cryoscopic) constant

· kf = 1.86 Km-1 for water Applications

T k m if

Page 40: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Osmotic Pressure

A pressure differential due to solvent molecules passing through a semipermeable membrane from a region of lower solute concentration to a region of higher solute concentration.

m R T

Page 41: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Osmotic Pressure

Page 42: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Osmotic Pressure

Page 43: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Osmotic Pressure

Page 44: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Osmotic Pressure

m R T

Page 45: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Osmotic PressureApplications

m R TMolecularweightdetermination

Biochemical

Why is physiological 0.9% saline solutionimportant in intravenous transfusions?

Page 46: Gas-Solution Processes Gas Solubility Raoult’s Law Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

04/18/23

Historical Perspective

Colligative properties were important to the early chemists because it provided information about the molecular weight or degree of ionization of the solute.