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Anda di halaman 1dari 95

Cecile N. Hurley

Chapter 5

Gases

Chapter Outline

• (5.1) Measurements on gases

• (5.2) The Ideal Gas Law

• (5.3) Gas law calculations

• (5.4) Stoichiometry of gaseous reactions

• (5.5) Gas mixtures: Partial pressures and mole

fractions

• (5.6) Kinetic theory of gases

• (5.7) Real gases

Measurements on Gases

• Quantities to be known to describe the state of the

gas

• Volume

• Amount

• Temperature

• Pressure

Volume, Amount, and Temperature

• Gases expand uniformly to fill the container in which

they are placed

• Volume of the container is the volume of the gas

• Volume may be in liters, mL, or cm3

• Moles (n) are used to express the matter in a gaseous

sample

mass

n=

MM

Kelvin scale

• Recall that TK = t°C + 273.15

Pressure

• Force per unit area

• In the English system, pounds per square inch or psi

• Atmospheric pressure is about 14.7 psi

• Mercury barometer is the device used to measure

atmospheric pressure

Figure 5.1 - A Mercury Barometer

The Barometer

• Measures pressure in relation to the height of a

column of liquid mercury

• First constructed by Evangelista Torricelli

• Consists of a closed gas tube filled with mercury

inverted over a pool of mercury

• Pressure exerted by the mercury column exactly

equals that of the atmosphere

• Height of the column is the measure of the

atmospheric pressure

• At or near sea level, the atmospheric pressure varies

from 740 - 760 mm

Figure 5.2 - The Manometer

Manometer

• Fluid used is mercury

• If the level in the inner tube (A) is lower than that in

the outer tube (B), the pressure of the gas is greater

than that of the atmosphere

• If the reverse is true, the pressure of the gas is less

than the atmospheric pressure

Units of Pressure

• Gas pressure is expressed in millimetres of

mercury (mm Hg)

• Torr - Pressure exerted by 1mm of mercury at

certain specified conditions, notably at 0° C

• Atmosphere (atm): Another unit commonly used to

measure gas pressure

• Also known as standard pressure

• 1 atm = 14.7 psi

• 1 atm = 760 mm Hg

Units of Pressure

• SI unit of measurement, the pascal (Pa)

• 1 Pa is the pressure exerted by a 0.1 mm high film of

water on the surface beneath it

• One bar = 105 Pa

• 1.013 bar = 1 atm = 760 mm Hg = 14.7 psi = 101.3 kPa

Example 5.1

• At room temperature, dry ice (solid CO2) becomes a

gas. At 77 °F, 13.6 oz of dry ice are put into a steel

tank with a volume of 10.00 ft3. The tank’s pressure

gauge registers 11.2 psi. Express the volume (V) of

the tank in liters, the amount of CO2 in grams and

moles (n), the temperature (T) in °C and K and the

pressure (P) in bars, mm Hg, and atmospheres

• Analysis

• Information given - volume (10.00 ft3); pressure (11.2

psi); temperature (77°F); mass of CO2 (13.6 oz)

Example 5.1

• Information implied - Molar mass of CO2

• Conversion factors for volume and mass formulas for

temperature conversion from °F to °C and from °C

to K

• Asked for

• Volume in L

• Pressure in atm, mm Hg, and bar

• Temperature in °C and K

• Moles of CO2

Example 5.1

• Strategy:

• Find the necessary conversion factors

• Use the temperature conversion formula

• Convert oz to grams and use the molar mass of CO2

as a conversion factor

• oz g mol

Example 5.1

• Solution:

28.32 L

• volume in L 10.00 ft × 3

3

= 283.2 L

1 ft

1 atm

= 0.762 atm

14.7 psi

• pressure in mm Hg

1 atm 760 mm Hg

11.2 psi × × = 579 mm Hg

14.7 psi 1 atm

Example 5.1

• pressure in bar 11.2 psi ×

1.013 bar

= 0.772 bar

14.7 psi

• temperature in °C °F = 1.8(°C) + 32;

77° = 1.8(°C) + 32;

°C = 25°C

K = 25°C + 273.15 = 298K

1g 1 mol

• mol CO2 13.6 oz × × = 8.77mol

0.03527 oz 44.01 g

Copyright ©2016 Cengage Learning. All Rights Reserved.

The Ideal Gas Law

• Volume is directly proportional to amount

• V = k1n (constant T, P)

• Volume is directly proportional to absolute

temperature

• V = k2T (constant n, P)

• Relation was first suggested by French scientists,

Jacques Charles and Joseph Gay-Lussac

• Referred to as Charles’s and Gay-Lussac’s law, or

simply Charles’s law

Figure 5.3 - Relation of Gas Volume (V) to Number of Moles (n)

and Temperature (T) at Constant Pressure (P)

Figure 5.4 - Illustration of Charles’s

Law

The Ideal Gas Law

• Volume is inversely proportional to pressure

k3

• V= (constant n, T)

P

• k3 is a constant

• Equation is of an inverse proportionality

• First established by Robert Boyle

• Equation is a form of Boyle’s law

Figure 5.5 - Relation of Gas Volume (V) to Pressure (P)

at Constant Temperature (T)

The Ideal Gas Law

• Combine k1, k2, and k3 into a new constant

• PV = nRT

• Ideal gas law

• R is the gas constant

L × atm

• Units of R: R = 0.0821

mol × K

Table 5.1 - Values of R in Different

Units

Standard Temperature and Pressure

• Standard Temperature and Pressure (STP)

• 1 atm pressure

• 273 K or 0°C

• At STP, one mole of any gas occupies a volume of

22.4 L

• Gas constant (R) can be calculated as

PV 1.00 atm × 22.4 L

R= = =0.0821 L . atm/(mol . K)

nT 1.00 mol × 273 K

Gas Law Calculations

• Final and initial state problems

• Calculation of P,V, n, or T

• Molar mass and density problems

Final and Initial State Problems

• In this type of problem, a gas undergoes a change

from its initial to its final state

• Involves the determination of the effects on V, P, n,

or T due to a change in one or more of these

variables

• Ideal gas laws are applied to these type of problems

• Two-point equations can be derived from the ideal

gas law to solve problems of this type

Example 5.2

• A sealed 15.0-L steel tank is used to deliver propane

(C3H8) gas. It is fitted with a pressure gauge and a

valve. The valve automatically opens to release gas

when the pressure in the tank goes above 1.200

atm. The tank is filled with 24.7 g of propane at 25

°C. The pressure gauge registers 0.915 atm.

• A) If the tank is heated to 55 °C, will the valve open

to release propane? (Assume that the expansion of

steel from an increase in temperature is negligible.)

Example 5.2

• Analysis:

• Information given - V (15.0 L); P (0.915 atm); T (25

°C); mass of propane (24.7 g) T (55 °C)

• Information implied - 2 sets of conditions for

temperature

• Asked for - Will the valve release gas?

Example 5.2

• Strategy:

• Given two sets of conditions, you need to use the

formula for initial state-final state conditions

• A sealed steel tank implies that the number of moles

and the volume are kept constant

• Make sure all temperatures are in K

• Find P and compare with 1.200 atm

Example 5.2

• Solution

• P2

V1P1 V2 P2 P1 P 2 0.915 P2

= = = P2 = 1.01 atm

n 1T1 n 2 T2 T2 T2 25 + 273 55 + 273

No. 1.01 atm < 1.200 atm

Example 5.2

• B) The temperature in the tank is increased to 200

°C. The valve opens and releases propane. How

many grams of propane are released?

• Analysis

• Information given

• Before T increase - V (15.0 L); P (0.915 atm); T (25

°C); mass of propane (24.7 g)

• After T increase - V (15.0 L); P (1.200 atm); T (200

°C); mass of propane (24.7 g)

• Information implied - molar mass of propane

• Asked for - mass of propane released

Example 5.2

• Strategy:

• Convert °C to K and mass of propane to mol

propane

• Given two sets of conditions, you need to use the

formula for initial state-final state conditions

• Find n2

• Convert n2 to mass of propane in the tank at 200 °C

and find the mass released by difference

Example 5.2

• Solution:

• T o

C K; 25 + 273 = 298; 200 + 273 = 473K

24.7 g × = 0.560 mol

44.1 g

• Initial conditions

P1 = 0.915 atm; T1 = 298 K; n1 = 0.560 mol;

V1 = 15.0 L

• Final conditions

P2 = 1.200 atm; T2 = 473 K; n2 = ?; V2 = 15.0 L

Example 5.2

• n2

= = ; n 2 = 0.463 mol

n1T1 n 2 T2 0.560 × 298 n 2 × 473

• (0.463 mol)(44.1 g/mol) = 20.4 g

• Mass to be released

• 24.7 – 20.5 = 4.3 g

Calculation of P, V, n or T

• In this type of problem, one of the state variables is

not known

• Done by direct substitution into the ideal gas law

• Take care to follow the units through the calculation

Example 5.3

• Sulfur hexafluoride is a gas used as a long-term

tamponade(plug) for a retinal hole to repair detached

retinas in the eye. If 2.50 g of this compound is

introduced into an evacuated 500.0-mL container at

83 °C, what pressure in atmospheres is

developed?

• Analysis

• Information given - V(500.0 mL); T(83°C); mass of

SF6 (2.50 g)

• Information implied - molar mass of SF6

ideal gas law (one state)

value for R

Copyright ©2016 Cengage Learning. All Rights Reserved.

Example 5.3

• Asked for - pressure (P) in atm

• Strategy:

• Change the given units to conform with the units for R

(mL → L; °C → K)

• You need to find n before you can use the ideal gas

law to find P

• Substitute into the ideal gas law: PV = nRT

Example 5.3

• Solution:

• Change in Units

500.0 mL = 0.5000 L; 83°C + 273 K = 356 K

• Find n

1 mol

2.50 g × = 0.0171 mol

146.07 g

• P

P= = = 1.00 atm

V 0.5000 L

Molar Mass and Density

• Density = mass/volume

• Molar mass has units of grams (mass) per mole

• Ideal gas law

• Number of moles which appear

• Moles, n, can be expressed as mass/MM

• There is also a volume term in the ideal gas law

Ideal Gas Law in Density Terms

mass

PV = RT

MM

mass P

density = = MM

V RT

• Pressure

• Temperature

• Molar mass

Figure 5.7 - Density of a Gas

Example 5.4

• Acetone has a density of 1.96 g/L at 95°C and 1.02

atm

• a) How many moles of acetone are there in a 1.00-L

flask under these conditions?

• Analysis:

• Information given - volume of the flask (1.00 L); T=

95°C + 273 = 368 K; density = 1.96 g/L

• Information implied - mass of acetone (1.96 g)

• Asked for - moles of acetone

Example 5.4

• Strategy:

• A gas occupies the volume of the flask; volume of

acetone = volume of flask

• Find n using the ideal gas law

• Solution:

• n

PV 1.02 × 1.00

n= = = 0.0338 mol

RT 0.0821 × 368

Example 5.4

• b) What is the molar mass of the acetone?

• Analysis

• Information given - from part (a) n = 0.0338 mol

• Information implied - mass of acetone (1.96 g)

• Asked for - molar mass

• Solution:

• molar mass

mass 1.96 g

MM = = = 58.0 g/mol

moles 0.0338 mol

Example 5.4

• c) Acetone contains the three elements, C, H, and O.

When 1.000 g of acetone is burned, 2.27 g of CO2

and 0.932 g of H2O are formed. What is the

molecular formula of acetone?

• Analysis

• Information given - molar mass of acetone (58.1

g/mol). The combustion of 1.00 g of sample yields

2.27 g CO2 and 0.932 g H2O.

• Information implied - mass of C, H, and O in 1.00 g

sample

• Asked for - molecular formula of acetone

Example 5.4

• Strategy:

• Convert the mass of the product of combustion to the

mass of the element

• Obtain the simplest formula for the compound

• Compare the simplest formula’s molar mass to the

molar mass obtained in part (b)

Example 5.4

• Solution:

• Mass of each element

• mass C

12.01 g C

2.27 g CO 2 × = 0.619 g

44.01 g CO 2

• mass H

2(1.008) g H

0.932 g H 2 O × = 0.104 g

18.02 g H 2 O

= 1.000 g - (0.619 + 0.104) g = 0.277 g

Example 5.4

• Moles of each element

0.619 g 0.104 g

C: =0.0515 mol; H: = 0.103 mol

12.01 g/mol 1.008 g/mol

0.277 g

O: =0.0173 mol

16.00 g/mol

• Atomic ratios

0.0515 0.104 0.0173

C: = 3; H: = 6; O: =1

0.0173 0.0173 0.0173

• Simplest formula

• C3H6O

Example 5.4

• MM of simplest formula

• 3(12.01) + 6(1.008) + 16.00 = 58.08 g/mol

• MM of vapor (from part (b))

• 58.1 g/mol

• Molecular formula

• C3H6O (simplest formula = molecular formula)

Stoichiometry in Gaseous Reactions

• Balanced equation can be used to relate moles or

grams of substances taking part in a reaction

• When gases are involved, the relations can be

extended to include volumes

• Ideal gas law is used

• First stoichiometric relationship to be discovered was

the law of combining volumes

• Volume ratio of any two gases in a reaction at constant

temperature and pressure is the same as the reacting

mole ratio

Figure 5.8 - Flowchart for Stoichiometry

Calculations Involving Gases

Example 5.5

• Hydrogen peroxide, H2O2, is a common bleaching

agent. It decomposes quickly to water and oxygen

gas at high temperatures.

2H 2 O 2 (l ) 2H 2O(l ) + O 2 (g )

and 0.934 atm when 1.27 L of H2O2 (d = 1.00 g/mL)

decompose?

Example 5.5

• Analysis

• Information given - temperature (78°C); pressure

(0.934 atm)

H2O2 - volume (1.27 L); density (1.00 g/mL)

• Information implied - mass and molar mass of H2O2

stoichiometric ratio of O2 to H2O2 (2 H2O2/1 O2)

• Asked for - Volume of oxygen

Example 5.5

• Strategy

• Change °C to K and L of H2O2 to mL. (Density is

given in g/mL.)

• Find the mass of H2O2. Note that you cannot directly

use the volume of H2O2 to calculate the volume of O2

because H2O2 is not a gas.

mass H 2 O 2

MM

mol H 2 O 2

stoichiometric

ratio

moles O 2

nRT/P

volume of oxygen

Example 5.5

• Solution:

• Mass H2O2

mass = (density)(volume) = (1.00 g/mL) (1.27 × 103 mL)

= 1.27 × 103 g

• Mol O2

1 mol H 2 O 2 1 mol O 2

1.27 × 103 g × × = 18.7 mol

34.02 g 2 mol H 2 O 2

• Volume O2

V= = = 576 L

P 0.934 atm

Figure 5.9 - Electrolysis of Water (H2O)

Gas Mixtures: Partial Pressures and Mole Fractions

mixtures of gases as well

• Partial pressure - Part of the total pressure due to

each gas in the mixture

• Sum of the partial pressures is the total pressure

Dalton’s Law of Partial Pressures

• Total pressure of a gas mixture is the sum of the

partial pressures of the gases in the mixture

• Consider a mixture of hydrogen and helium

• PH2 = 2.46 atm

• PHe = 3.69 atm

• Ptotal = 6.15 atm

Wet Gases; Partial Pressure of Water

• P H2O is the vapor pressure of water

• P H2O is dependent on temperature

• Consider the H2 gas collected by bubbling through water

Ptot = PH2O + PH2

vapor pressure of liquid water

• Vapor pressure of a substance is the pressure of the

gaseous form of that substance

• Intensive property

• Depends on temperature

Figure 5.10 - Collecting a Gas by

Water Displacement

Example 5.8

• A student prepares a sample of hydrogen gas by

electrolyzing water at 25°C. She collects 152 mL of

H2 at a total pressure of 758 mm Hg. Using Appendix

1 to find the vapor pressure of water at 25°C,

calculate

• (a) the partial pressure of hydrogen

• (b) the number of moles of hydrogen collected

• Analysis

• Information given - VH2 (152 mL); pressure (758 mm

Hg); temperature (25°C)

Example 5.8

• Information implied - vapor pressure of water at

25°C

Volume and temperature are constant

• Asked for - (a) PH2

(b) nH2

• Strategy

• Recall that H2 and H2O(g) contribute to the total

pressure Ptot.

• Use Dalton’s law - Ptot = P1 + P2 + . . .

• Use the ideal gas law to calculate nH2 at PH2

Example 5.8

• Solution:

• PH2

Ptot = PH2 + PH2O

PH2 = 758 mm Hg - 23.76 mm Hg = 734 mm Hg

• nH2

PH2 V [(734/760) atm](0.152 L)

n H2 = = = 0.00600 mol

RT (298 K)(0.0821 L . atm/mol . K)

Partial Pressure and Mole Fraction

• One can rearrange the ideal gas law for a mixture containing

two gases, A and B

PA n A

=

Ptot n tot

• Partial pressure of gas A is its mole fraction times the total

pressure

PA = X A Ptot

Kinetic Theory of Gases

• Molecular model

• Gases are mostly empty space

• Total volume of the molecules is small

• Gas molecules are in constant, chaotic motion

• Collisions of gas particles are elastic

• Gas pressure is caused by collisions of molecules

with the walls of the container

Figure 5.11 - The Kinetic Molecular Model of a

Gas

Expression for Pressure, P

Nmu 2

P=

3V

• M is the mass of the gas particle

• u is the average speed of a gas particle

• Notes

• N/V is the concentration of gas particles

• mu2 is a measure of the energy of the collisions

Average Kinetic Energy of Translational

Motion, Et

3RT

Et =

2N A

• Notes

• R is the gas constant

• T is the temperature in Kelvin

• NA is the Avogadro’s number

Average Kinetic Energy of Translational

Motion, Et

• At a given temperature, molecules of different gases

must have the same average kinetic energy of

translational motion

• Average translational kinetic energy of a gas

molecule is directly proportional to the Kelvin

temperature, T

Average Speed, u

1

3RT 2

u=

MM

• Expression for the average speed of gas molecules

• Directly proportional to the square root of the absolute

temperature

• Inversely proportional to the square root of molar mass

Figure 5.12 - Relation of Molecular Speed to

Molar Mass

Example 5.10

• Calculate the average speed, u, of an N2 molecule at

25°C.

• Analysis

• Information given - temperature (25°C)

• Information implied

R = 8.31 × 103 g . m 2 /s 2 . mol . K

MM of N2

• Asked for - Average speed, u, of N2 at 25°C

Example 5.10

• Strategy:

• Change T to the appropriate units

• Note the units of the constant R 1

3RT 2

• Substitute into the equation - u =

MM

• Solution:

• Average speed

1

3 g . m2 2

3 × 8.31 × 10 2

× 298K

u= s . mol . K = 515 m/s

g

28.02

mol

Effusion of Gases

• Diffusion

• Gases move through space from a region of high

concentration to a region of low concentration

• Relatively slow process

• Effusion

• Flow of gas molecules at low pressures through tiny

pores or pin holes

• Easier to analyse using kinetic theory

Effusion of Gases

• Factors affecting rate of effusion

• Pressure of the gases

• Relative speed of the particles

Graham’s Law of Effusion

1

rate of effusion of B MMA 2

rate of effusion of A MMB

effusion of a gas, in moles per unit time, is inversely

proportional to the square root of its molar mass

Figure 5.13 - Effusion of Gases

Example 5.11

• In an effusion experiment, argon gas is allowed to

expand through a tiny opening into an evacuated

flask of volume 120 mL for 32.0 s, at which point the

pressure in the flask is found to be 12.5 mm Hg. This

experiment is repeated with a gas X of unknown

molar mass at the same T and P. It is found that the

pressure in the flask builds up to 12.5 mm Hg after

48.0 s. Calculate the molar mass of X.

Example 5.11

• Analysis:

• Information given - volume of both flasks (120 mL);

pressure in both flasks (12.5 mm Hg); time for Ar

effusion (32.0 s); time for gas (X) effusion (48.0 s)

• Information implied - Temperature, pressure, and

volume are the same for both flasks

rate of effusion for each gas

MM of argon

• Asked for - MM of X

Example 5.11

• Strategy:

• Since T, P, and V are the same for both gases, the

number of moles of gas in both flasks is the same

nAr = nX = n

• The rate of effusion is in mol/time

n Ar nX n

rate = = =

time time time

• Substitute into Graham’s law of effusion, where A =

gas X and B = Ar

1/2

rate B MM A rate Ar MM X

= =

rate A MM B rate X MM Ar

Example 5.11

• Solution:

• Rates

n n

rateX = rateAr =

48.0 s 32.0 s

• MMX

n 1/2 1/2

32.0 s = MM MM X

1.50 =

X

n

39.95 g/mol 39.95 g/mol

48.0 s

2

MM

1/2

MM X

1.50 =

2 X

2.25 = MM X = 89.9 g/mol

39.95 g/mol 39.95 g/mol

Application of Effusion

• Used to separate U-238 from U-235

• Isotopes have the same chemical properties and so

cannot be separated by chemical means

• Preliminary experiments indicated that 238UF6 could

be separated from 235UF6 by effusion

• Separation factor is small, as the rates of effusion are

nearly identical

Distribution of Molecular Speeds

• In a gas sample at any instant, gas molecules are

moving at a variety of speeds

• Speed and direction of motion of a particle are

constantly changing

• James Clerk Maxwell developed a mathematical

expression for the distribution known as the Maxwell

distribution

• Molecules have speeds rather close to the average

value

Figure 5.14 - Distribution of Molecular Speeds of

Oxygen Molecules at 25°C and 1000°C

Distribution of Molecular Speeds

• Plot the fraction of molecules having a given speed

vs. the molecular speed

• Curve that results has a maximum in the number of

molecules with the given speed

• Probable speed of molecules

• As the temperature increases

• Speed of the molecules increases

• Distribution curve for molecular speeds shifts to the

right and becomes broader

Example 5.12

• Consider the two boxes A and B shown below. Box

B has a volume exactly twice that of box A. The

green circles and red circles represent one mole of

HCl and He, respectively. The two boxes are at the

same temperature.

Example 5.12

• Compare the pressures of the gases in the two

containers

• Compare the densities of the two gases

• Compare the number of atoms in the two boxes

• If the HCl in box A were transferred to box B, what

would be the mole fraction of HCl in the mixture?

• Which of the two gases effuses faster?

Example 5.12

• Solution:

• Since n/V and T are the same in both cases, pressure

P = nRT/V is the same for the two gases

• The mass of HCl is 2(36.5 g) = 73.0 g; that of He is

4(4.00 g) = 16.0 g. Since 73.0 g/V > 16.0 g/2V, HCl

has the higher density

• Two moles of diatomic HCl contain the same number

of atoms as four moles of He

• XHCl = 2/6 = 1/3

• Because HCl and He are at the same pressure, the

lighter gas, He, effuses faster

Real Gases

• Deviate at least slightly from the ideal gas law

• Molar volume of a gas at STP is 22.4 L from the

ideal gas law

• Deviations from ideality become larger at high

pressures and low temperatures

• Closer a gas is to the liquid state, the more it will

deviate from the ideal gas law

Table 5.2 - Real Versus Ideal Gases, Percent

Deviation* in Molar Volume

Real Gases

• Gases can be liquefied by

• Lowering the temperature

• Increasing the pressure

• Deviations from the ideal gas law arise because they

neglect

• Attractive forces between gas particles

• Finite volume of gas particles

Attractive Forces

• Observed molar volume for gases is lower than that

calculated by the ideal gas law

• Forces between particles pull the particles together

• Volume occupied by the gas is then decreased

• This is a negative deviation from the ideal gas law

Particle Volume

• Consider a plot of the observed molar volume/ideal

molar volume for methane at 25°

• Up to 150 atm, the deviation from ideality steadily

increases

• Above 150 atm, molar volume/ideal molar volume

increases

• Ratio becomes 1 at around 350 atm pressure

• Above 350 atm, methane shows a positive deviation

from the ideal gas law

• This behavior is observed with all gases and is not

unique to methane

Figure 5.11 - Deviation from Ideal Volume

Key Concepts

• Convert between P, V, T, and amount of gas

• Use of the ideal gas law to:

• Solve initial and final state problems

• Calculate P, V, T, or n

• Calculate density or molar mass

• Relate amounts and volumes of gases in reactions

• Use Dalton’s law

• Calculate the speed of gas molecules

• Use Graham’s law to relate the rate of effusion to

the molar mass of a gas

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