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You are on page 1of 48

**Course # 111, two credits
**

Second Semester 2009

King Saud bin Abdulaziz University for Health Science

**Textbook: Principles of Modern Chemistry
**

by David W. Oxtoby, H. Pat Gillis, and Alan Campion (6 edition; 2007)

Dr. Rabih O. Al-Kaysi

Ext: 47247

Email: kaysir@ksau-hs.edu.sa

Lectures 10

Gases

Gases You Have Encountered

Characteristics of Gases

• Gases always form homogeneous mixtures with other gases

• Gases are highly compressible and occupy the full volume of their

containers. (Chapter 1)

• When a gas is subjected to pressure, its volume decreases.

• .

Pressure

**• Pressure is the force acting on an object per unit area:
**

F

P=

A

• Gravity exerts a force on the earth’s atmosphere

• A column of air 1 m2 in cross section exerts a force of 105

N.

• The pressure of a 1 m2 column of air is 100 kPa.

• SI Units: 1 N = 1 kg.m/s2; 1 Pa = 1 N/m2.

Atmosphere Pressure and The

Barometer

• If a tube is inserted into a container of mercury open to

the atmosphere, the mercury will rise 760 mm up the

tube.

• Atmospheric pressure is measured with a barometer.

• Standard atmospheric pressure is the pressure required to

support 760 mm of Hg in a column.

• Units: 1 atm = 760 mmHg = 760 torr = 1.01325 × 105

Pa = 101.325 kPa.

Class Guided Practice Problem

**Class Practice Problem
**

• (c) Convert 147.2 kPa to (1) atm and (2) torr

Atmosphere Pressure and The

Manometer

• The pressures of gases not open

to the atmosphere are measured

in manometers.

• A manometer consists of a bulb

of gas attached to a U-tube

containing Hg:

– If Pgas < Patm then Pgas + Ph2 = Patm .

– If Pgas > Patm then Pgas = Patm + Ph2.

(See example problem 10.2)

Defining States of Gases

• Gas experiments revealed that four variables will affect

the state of a gas:

• Temperature, T

• Volume, V

• Pressure, P

• Quantity of gas present, n (moles)

• These variables are related through equations know as the

gas laws.

The Ideal Gas Equation

• Consider the three gas laws.

• Boyle’s Law: 1

V∝ (constant n, T )

P

• Charles’s Law: V ∝ T (constant n, P)

• Avogadro’s Law: V ∝ n (constant P, T )

• We can combine these into a general gas law:

nT

V∝

P

The Gas Laws: Boyle’s Law

The Pressure-Volume Relationship:

• Weather balloons are used as a practical consequence to the

relationship between pressure and volume of a gas.

• As the weather balloon ascends, the volume increases.

• As the weather balloon gets further from the earth’s surface,

the atmospheric pressure decreases.

• Boyle’s Law: the volume of a fixed quantity of gas is

inversely proportional to its pressure.

• Boyle used a manometer to carry out the experiment.

Boyle’s Law

The Pressure-Volume Relationship

• Mathematically:

1

V = constant × P

V =c

ons

tan

t

P

• A plot of V versus P is a hyperbola.

• Similarly, a plot of V versus 1/P must be a straight line

passing through the origin.

• The Value of the constant depends on the temperature

and quantity of gas in the sample.

Charles’s Law

The Temperature-Volume Relationship:

• We know that hot air balloons expand when they are

heated.

• Charles’s Law: the volume of a fixed quantity of gas at

constant pressure increases as the temperature increases.

• Mathematically:

V

V = constant × T = constant

T

Plotting Charles’s Law

**• A plot of V versus T is a straight line.
**

• When T is measured in °C, the intercept on the

temperature axis is -273.15°C.

• We define absolute zero, 0 K = -273.15°C.

• Note the value of the constant reflects the assumptions:

amount of gas and pressure.

All gases will solidify or liquefy before reaching zero volume.

Avogadro’s Law

The Quantity-Volume Relationship:

• Gay-Lussac’s Law of combining volumes: at a given

temperature and pressure, the volumes of gases which

react are ratios of small whole numbers.

Avogadro’s Law

• Avogadro’s Hypothesis: equal volumes of gas at the

same temperature and pressure will contain the same

number of molecules.

• Avogadro’s Law: the volume of gas at a given

temperature and pressure is directly proportional to the

number of moles of gas.

Expressing Avogadro’s Law

• Mathematically:

V = constant × n

• We can show that 22.4 L of any gas at 0°C contain 6.02 × 1023

gas molecules.

The Ideal Gas Constant

• If R is the constant of proportionality (called the gas

constant), then

nT

V = R

P

• The ideal gas equation is:

PV = nRT

L ⋅ atm J

R = 0.08206 = 8.314

mol ⋅ K mol ⋅ K

Applying The Ideal Gas Equation

**• We define STP (standard temperature and pressure) =
**

0°C, 273.15 K, 1 atm.

• Volume of 1 mol of gas at STP is:

**nRT (1 mol)( 0.08206 L·atm/mol·K )( 273.15 K )
**

V= = = 22.41 L

P 1.000 atm

Relating the Ideal-Gas Equation and

the Gas Laws

• If PV = nRT and n and T are constant, then PV = constant and we

have Boyle’s law.

• Other laws can be generated similarly.

• In general, if we have a gas under two sets of conditions, then

P1V1 P2V2

=

n1T1 n2T2

Class Guided Practice Problem

**• A sample of argon gas is confined to a 1.00-L tank at
**

27.0 oC and 1 atm. The gas is allowed to expand into a

larger vessel. Upon expansion, the temperature of the gas

drops to 15.0 oC, and the pressure drops to 655 torr.

What is the final volume of the gas?

**Two ways to work this problem.
**

Molar Mass

• Density has units of mass over volume.

• Rearranging the ideal-gas equation with M as molar mass

we get

PV = nRT

n P

=

V RT

nM PM

=d =

V RT

Gas Densities

• The molar mass of a gas can be determined as follows:

dRT

M=

P .

Class Guided Practice Problem

**• What is the density of carbon tetrachloride vapor at 714
**

torr and 125 oC?

Volumes of Gases in Chemical

Reactions

• The ideal-gas equation relates P, V, and T to number of

moles of gas.

• The n can then be used in stoichiometric calculations

Class Guided Practice Problem

**• The safety air bags in automobiles are inflated by
**

nitrogen gas generated by the rapid decomposition of

sodium azide, NaN3:

2 NaN3(s) → 2 Na(s) + 3N2(g)

If an air bag has a volume of 36 L and is filled with

nitrogen gas at a pressure of 1.15 atm at a temperature of

26 oC, how many grams of NaN3 must be decomposed?

Gas Mixtures and Partial Pressures

• Since gas molecules are so far apart, we can assume they

behave independently.

• Dalton’s Law: in a gas mixture the total pressure is given by

the sum of partial pressures of each component:

Ptotal = P1 + P2 + P3 +

• Each gas obeys the ideal gas equation:

RT

Pi = ni

V

• Combining the equations we get:

RT

Ptotal = ( n1 + n2 + n3 + )

V

Collecting Gases over Water

Collecting Gases over Water

• It is common to synthesize gases and collect them by

displacing a volume of water.

• To calculate the amount of gas produced, we need to

correct for the partial pressure of the water:

**Ptotal = Pgas + Pwater
**

Class Guided Practice Problem

• A gaseous mixture made form 6.00g O2 and 9.00g CH4 is

placed in a 15.0-L vessel at 0 oC. What is the total

pressure in the vessel?

Kinetic Molecular Theory

• Theory developed to explain gas behavior.

• Theory of moving molecules.

• Assumptions:

– Gases consist of a large number of molecules in constant

random motion.

– Volume of individual molecules negligible compared to

volume of container.

– Intermolecular forces (forces between gas molecules)

negligible.

Kinetic Molecular Theory

• Assumptions:

– Energy can be transferred between molecules, but total kinetic

energy is constant at constant temperature.

– Average kinetic energy of molecules is proportional to

temperature.

• Kinetic molecular theory gives us an understanding of

pressure and temperature on the molecular level.

• Pressure of a gas results from the number of collisions

per unit time on the walls of container.

Kinetic Molecular Theory

• Magnitude of pressure

given by how often and

how hard the molecules

strike.

• Gas molecules have an

average kinetic energy.

• Each molecule has a

different energy.

Kinetic Molecular Theory

**• As kinetic energy increases, the velocity of the gas
**

molecules increases.

• Root mean square speed, u, is the speed of a gas molecule

having average kinetic energy.

• Average kinetic energy, ε , is related to root mean square

speed:

ε = mu1

2

2

Application to Gas Laws

• As volume increases at constant temperature, the average

kinetic of the gas remains constant. Therefore, u is

constant. However, volume increases so the gas

molecules have to travel further to hit the walls of the

container. Therefore, pressure decreases.

• If temperature increases at constant volume, the average

kinetic energy of the gas molecules increases. Therefore,

there are more collisions with the container walls and the

pressure increases.

Real Gases: Deviations from Ideal

Behavior

• From the ideal gas equation, we have

PV

=n

RT

• For 1 mol of gas, PV/RT = 1 for all pressures.

• In a real gas, PV/RT varies from 1 significantly.

• The higher the pressure the more the deviation from ideal

behavior.

Real Gases: Deviations from Ideal

Behavior

• From the ideal gas equation, we have

PV

=n

RT

• For 1 mol of gas, PV/RT = 1 for all temperatures.

• As temperature increases, the gases behave more ideally.

• The assumptions in kinetic molecular theory show where

ideal gas behavior breaks down:

– the molecules of a gas have finite volume;

– molecules of a gas do attract each other

• .

Real Gases: Deviations from Ideal

Behavior

• As the pressure on a gas increases, the molecules are

forced closer together.

• As the molecules get closer together, the volume of the

container gets smaller.

• The smaller the container, the more space the gas

molecules begin to occupy.

• Therefore, the higher the pressure, the less the gas

resembles an ideal gas.

Real Gases: Deviations from Ideal

Behavior

• As the gas

molecules get

closer together,

the smaller the

intermolecular

distance.

Real Gases: Deviations from Ideal

Behavior

• The smaller the distance between gas molecules, the

more likely attractive forces will develop between the

molecules.

• Therefore, the less the gas resembles and ideal gas.

• As temperature increases, the gas molecules move faster

and further apart.

• Also, higher temperatures mean more energy available to

break intermolecular forces.

Real Gases: Deviations from Ideal

Behavior

• Therefore, the higher the

temperature, the more ideal the

gas.

The van der Waals Equation

• We add two terms to the ideal gas equation one to correct

for volume of molecules and the other to correct for

intermolecular attractions

• The correction terms generate the van der Waals

equation:

nRT n2a

P= − 2

V − nb V

where a and b are empirical constants.

The van der Waals Equation

nRT n2a

P= − 2

V − nb V

Corrects for Corrects for

molecular volume molecular attraction

n2a

P + 2 (V − nb ) = nRT

V

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