Gases

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Gases

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• Properties of Gases

• Gas Laws (pressure, volume, temperature,

moles)

• Gases in Chemical Reactions

• The Kinetic Model of Gases

Gaseous elements

Pressure = Force/Area

Boyle’s Law

V ~ 1/P

is released into a larger

container,

how much force does it

exert?

If the volume of a gas is constrained to a smaller container,

how much force does it exert?

P ~ 1/V

Boyle’s Law:

P1V1 = P2V2

Relationship V1

between

volume and

pressure. P1

P1V1 = P2V2

Decrease volume

more collisions

V2

• Ex. 1 A sample of gas occupies 21 liters at a

pressure of 2.2 atm. What would be the volume if

the pressure was increased to 6.2 atm?

At what pressure would it occupy 14.5 L?

If the temperature of gas is increased, how will its volume respond

(if the pressure is kept constant)?

Charle’s Law:

V1/T1 = V2 / T2

Gas 1

Gas 2

Gas 3

Gas 4

would have zero volume!

If a gas is heated, how much force does it exert

(if the volume is kept constant)?

P~T

Combined Gas Law

(Boyle and Charle’s)

P1 V1 = P2 V2

T1 T2

Re-cap of Gases:

Boyle’s Law: Charles’s Law:

P1 V1 = P2 V2 V1/T1 = V2 / T2

P1 V1 = P2 V2

T1 T2

2) Watch your units! (K, L, atm)

One standardized set of conditions =

“STP”

• 0o C (273 K)

• Ex. 3 A balloon filled with He occupies 413 mL at

100.oC. At what temperature would it occupy 577 mL if

the pressure was constant?

at 27oC at 1200 T. What volume would it occupy at STP?

How much volume does 1 mole of gas occupy

at 0o C, 1 atm?

will be occupied by:

one mole N2

one mole O2

one mole H2

How much volume does 1 mole of gas occupy

at 0o C, 1 atm?

Liters

Ex. 5 What is the density of a gas that has a

molar mass of 44.01 g/mol at STP?

Ideal Gas Law: PV = nRT

(where n = moles)

What is “R”?

“STP” = 0 o C and 1 atm

• Ex. 6 What is the volume of a balloon filled with 32.02

grams of Helium when the atmospheric pressure is 722 torr

and the temperature is 40o C?

prior to a football game. Its volume is 7601 ft3. How

many grams of He are needed for a pressure of 740 torr at

22o C?

(1 ft3 = 28.3 L)

• Ex. 9 A 0.723 g sample of a gas occupies

176 mL at 100.o C and 750. torr. What is its

molar mass?

Stoichiometric Calculations Involving Gases

C3H8 + 5O2 3CO2 + 4H2O

25.0 g of propane produces how many moles of CO2?

25.0 g of propane produces how many liters of CO2 at STP?

How many grams of propane are need to react with

50.0 L of O2 at 25o C and 1.0 atm?

Key Concepts:

• Ideal Gas Law PV = nRT

An airbag inflates in less than 50 msec by the reaction of NaN3

to produce Na and nitrogen gas:

NaN3 Na + N2

The volume of the airbag is about 30 L when inflated, and it is

filled to a pressure of 1.4 atm. How many grams of NaN3 must

be used for each air bag? The molar mass of NaN3 is 65.1

g/mole. Assume the process occurs at room temperature.

Gas mixtures

• Dalton’s Law of partial pressures

The total pressure of a mixture of gases equals the

sum of the pressures that each would exert if it

were present alone

PT=P1+P2+P3+….Pn

9.00g methane placed in a 15L vessel at 0oC. What is the partial

pressure of each gas and the total pressure in the vessel?

Dalton’s law of

partial pressures

PT = Pa + Pb + Pc + Pd = …

is also equal to: nXRT/V

Mole Fractions

• The ratio n1/nT is called the mole fraction (denoted x1), a

dimensionless number between 0 and 1.

P1 n1RT / V n1

PT nT RT / V nT

n1

P1 PT

nT

Mole fraction of N2 in air is 0.78, therefore if the total

barometric pressure is 760 torr, the partial pressure of N2 is

(0.78)(760) = 590 torr.

Kinetic –Molecular Theory

Theory describing why gas laws are obeyed (explains both pressure and

temperature of gases on a molecular level).

• Complete form of theory, developed over 100 years or so, published by

Clausius in 1857.

Gases consist of large numbers of molecules that are in continuous,

random motion

Volume of all molecules of the gas is negligible, as are

attractive/repulsive interactions

Interactions are brief, through elastic collisions (average kinetic energy

does not change)

Average kinetic energy of molecules is proportional to T, and all gases

have the same average kinetic energy at any given T.

Because each molecule of gas will have an individual kinetic energy, and thus

individual speed, the speed of molecules in the gas phase is usually characterised

by the root-mean-squared (rms) speed, u,(not the same though similar to the

average speed). Average kinetic energy є = ½mu2

Application to Gas Laws

• Increasing V at constant T:

Constant T means that u is unchanged.

But if V is increased the likelihood of

collision with the walls decreases,

thus the pressure decreases (Boyle’s

Law)

• Increasing T at constant V:

Increasing T increases u, increasing

collisional frequency with the walls,

thus the pressure increases (Ideal Gas

Equation).

• Ex. 10 A 20.5 L bulb contains 0.200 moles of methane,

0.300 moles of hydrogen, and 0.400 moles of nitrogen at

20.0 o C. It is stinky and explosive. What is the pressure

inside the bulb? How much pressure is contributed by

each of the three gases?

A second tank contains 3.00 L of O2 at 24.0 atm. What

pressure is attained when the valve between the tanks is

opened?

Mole fraction: the portion of a specific substance

within a mixture

Kinetic model of gases

each dot is

one gas

molecule

The Kinetic-Molecular Theory

• The basic assumptions of kinetic-molecular theory

are:

• Postulate 1

– Gases consist of discrete molecules that are relatively far

apart.

– Gases have few intermolecular attractions.

– The volume of individual molecules is very small compared

to the gas’s volume.

• Proof - Gases are easily compressible.

The Kinetic-Molecular Theory

• Postulate 2

– Gas molecules are in constant, random, straight

line motion with varying velocities.

• Proof - Brownian motion displays

molecular motion.

The Kinetic-Molecular Theory

• Postulate 3

– Gas molecules have elastic collisions with

themselves and the container.

– Total energy is conserved during a collision.

• Proof - A sealed, confined gas exhibits no

pressure drop over time.

The Kinetic-Molecular Theory

• Postulate 4

– The kinetic energy of the molecules is

proportional to the absolute temperature.

– The average kinetic energies of molecules of

different gases are equal at a given

temperature.

• Proof - Brownian motion increases as

temperature increases.

The Kinetic-Molecular Theory

• The kinetic energy of the molecules is

proportional to the absolute temperature. The

kinetic energy of the molecules is proportional to

the absolute temperature.

• Displayed in a Maxwellian distribution.

The Kinetic-Molecular Theory

• The gas laws that we have looked at earlier in this chapter are

proofs that kinetic-molecular theory is the basis of gaseous

behavior.

• Boyle’s Law

– P 1/V

– As the V increases the molecular collisions with container

walls decrease and the P decreases.

• Dalton’s Law

– Ptotal = PA + PB + PC + .....

– Because gases have few intermolecular attractions, their

pressures are independent of other gases in the container.

• Charles’ Law

– VT

– An increase in temperature raises the molecular velocities,

thus the V increases to keep the P constant.

The Kinetic-Molecular Theory

• The root-mean square velocity of gases is a

very close approximation to the average gas

velocity.

• Calculating the root-mean square velocity is

simple:

3RT

u rms

Mm

• To calculate this correctly:

– The value of R = 8.314 kg m2/s2 K mol

– And M must be in kg/mol.

The Kinetic-Molecular Theory

• Example 12-17: What is the root mean square

velocity of N2 molecules at room T, 25.0oC?

kg m 2

3 8.314 2 298 K

sec K mol

u rms

0.028 kg / mol

515 m / s = 1159 mi / hr

The Kinetic-Molecular Theory

• What is the root mean square velocity of

He atoms at room T, 25.0oC?

The Kinetic-Molecular Theory

kg m

2

3 8.314 2 298 K

sec K mol

u rms

0.004 kg / mol

1363 m / s = 3067 mi / hr

• Can you think of a physical situation that proves

He molecules have a velocity that is so much

greater than N2 molecules?

• What happens to your voice when you breathe

He?

Diffusion and Effusion of Gases

• Diffusion is the intermingling of gases.

• Effusion is the escape of gases through

tiny holes.

Diffusion and Effusion of Gases

• This is a demonstration of diffusion.

Diffusion and Effusion of

Gases

• The rate of effusion is inversely proportional

to the square roots of the molecular weights

or densities.

R1 M2

R2 M1

or

R1 D2

R2 D1

Diffusion and Effusion of Gases

• Calculate the ratio of the rate of effusion of He

to that of sulfur dioxide, SO2, at the same

temperature and pressure.

R He M SO 2

R SO 2 M He

641

. g / mol

4.0 g / mol

16 4 R He 4R SO 2

Diffusion and Effusion of Gases

• Example 12-16: A sample of hydrogen, H2, was found to

effuse through a pinhole 5.2 times as rapidly as the same

volume of unknown gas (at the same temperature and

pressure). What is the molecular weight of the unknown

gas?

R H2 M unk

R unk M H2

M unk

5.2

2.0 g/mol

M unk

27

2.0 g/mol

M unk 27( 2.0 g/mol) = 54 g/mol

Real Gases:

Deviations from Ideality

• Real gases behave ideally at ordinary

temperatures and pressures.

• At low temperatures and high pressures real

gases do not behave ideally.

• The reasons for the deviations from ideality are:

1. The molecules are very close to one another, thus

their volume is important.

2. The molecular interactions also become important.

Real Gases:

Deviations from Ideality

• van der Waals’ equation accounts for the

behavior of real gases at low temperatures and

high pressures.

n 2a

2

P + V nb nRT

V

• The van der Waals constants a and b take into

account two things:

1. a accounts for intermolecular attraction

2. b accounts for volume of gas molecules

• At large volumes a and b are relatively small

and van der Waal’s equation reduces to ideal

gas law at high temperatures and low

pressures.

Real Gases:

Deviations from Ideality

• What are the intermolecular forces in

gases that cause them to deviate from

ideality?

1. For nonpolar gases the attractive forces

are London Forces

2. For polar gases the attractive forces are

dipole-dipole attractions or hydrogen

bonds.

Real Gases:

Deviations from Ideality

• Example 12-19: Calculate the pressure exerted by

84.0 g of ammonia, NH3, in a 5.00 L container at

200. oC using the ideal gas law.

1 mol

n = 84.0 g NH3 4.94 mol

17.0 g

L atm

4.94 mol 0.0821 473 K

P=

nRT

mol K

V 5.00 L

P 38.4 atm

Real Gases:

Deviations from Ideality

• Solve Example 12-19 using the van der

Waal’s equation.

L2 atm

n = 4.94 mol a = 4.17 b = 0.0371 L

mol 2 mol

n 2a

P + 2 V - nb nRT

V

nRT n 2a

P= 2

V - nb V

Real Gases:

Deviations from Ideality

4.94 mol 0.0821 473K 4.94 mol 4.17

L atm

2 L2 atm

P mol K

mol 2

5.00 L (4.94 mol )(0.0371 mol )

L

5.00 L 2

191.8 L atm

P 4.07 atm (39.8 atm 4.1 atm )

4.817 L

P 35.7 atm which is a 7.6% difference from ideal

“Real” gases

• Deviations from ideal behavior as gases are

exposed to:

– high pressures

– low temperatures

temperatures???)

• The molar volume is not constant as is expected for ideal

gases.

• These deviations due to an attraction between some

molecules.

• Finite molar molecular volume.

• For compounds that deviate from ideality the van der

Waals equation is used:

n 2a

P + (V - nb) = nRT

2

V

gas.

• Applicable at high pressures and low temperatures.

Ideal: PV = nRT

Ideal: P = nRT/V

Real:

P = nRT/(V – nb) - a 2

n /V 2

“Real” gases

Ex. 13 Calculate the pressure exerted by 5.00 moles

of NH3 in a 1.00 L vessel at 25.0oC assuming ideal

and non-ideal behavior.

Compression Factor

Variation of Z with Pressure

At 0 C

molar volume

Z

molar volume perfect gas

pV

Z

RT

Low pressures, Z=1, all gases ideal

At high pressures, Vreal >Videal ; Z>1

repulsive forces dominate

Low pressure, Vreal <Videal, Z< 1

attractive forces dominate

Low temperatures -> molecules moving

less rapidly more influenced by

attractive forces

Van der Waals Equation (1873)

2

RT a nRT n

p 2 p a

Vm b Vm V nb V

a reflects how strongly molecules attract each other

b corrects for the molecule’s size

“Derivation” of vdw Eq. State

Repulsive interactions cause molecules to behave as

impenetrable spheres

Molecules restricted to smaller volume V-nb, where nb is

volume molecules take up

force of each collision – both reduced by attractive forces

proportional to molar concentration (n/V)

Pressure is then reduced according to a(n/V)2

Phase Transition: Condensation

Imagine you are compressing gas with piston

At C, piston slides without further change in

pressure

Liquid begins to appear – Two phases coexist

Going to E – amount of liquid increases

Pressure along CDE is vapour pressure

At E, sample is liquid – now the compressibility

changes ….

systems, which exhibit a rich variety of phase

transitions …

Experimental isotherms of

CO2 at several temperatures.

Critical Constants

The `critical isotherm', the isotherm

at the critical temperature Tc, is at

31.04 C. The critical point is

marked with a star.

Critical pressure Pc

Critical molar volume Vc

Tc, Pc,Vc critical constants

does not appear – these highly

dense materials are called

“supercritical fluids” and their

properties are a subject of intense

current research

Virial Equation of State

Most fundamental and theoretically sound

Polynomial expansion – Viral Expansion

PV

Z 1 B2 P ( P) P B3 P ( P) P 2 ...

RT

PV B (T ) B3V (T )

Z 1 2V 2

...

RT V V

Also allow derivation of exact correspondence between

virial coefficients and intermolecular interactions

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