Chapter 2

Gases
Characteristics of gases
Physical behavior of Gases
The Simple Gas Laws
The Ideal Gas Equation
Dalton's law
Grahams lawof Effusion
Kinetic-Molecular Theory of Gases

1. Physical behavior of gases

For gas sample there are three measurable variables
1. Volume, V, is the capacity of the container enclosing it. Unit
of volume: is the cubic meter (m3), a cubic decimeter (dm3), or
liter.
For smaller volumes we will use the cubic centimeter (cm3), which is
the same as the milliliter (ml).
2. Temperature: Three temperature scales,
Fahrenheit (F),
Celsius (C),
Kelvin K (no degree symbol)
Always use K when performing calculations with the gas law
equations.
K = (C) + 273.15
Example: C = 20 K = 293.15
Absolute or Kelvin scale: Temperature scale that has -273.15 C as
its zero. Temperature interval of one Kelvin equals one degree
Celsius. 1 K = 1 C
3. Pressure, P, is defined as force per unit area
(F = force A = area)

The molecules in a gas are in constant

motion. The gaseous atoms are
colliding with each other and the walls
of the container. "Pressure" is a
measure of the collisions of the
atoms with the container.
Barometer

Barometer is a device used to measure the pressure exerted by the

atmosphere.
Height of mercury varies with atmospheric conditions and with
altitude
Mercury Barometer
Standard atmospheric pressure is the

pressure required to support 760 mm

of Hg in a column.
There are several units used for pressure:
Pascal (Pa), N/m2
Millimeters of Mercury (mmHg) = torr
Atmospheres (atm) = 760 mmHg = 100 KPa

Physical Chemistry First Year First semester Page 13

Measurement of Gas Pressure

Manometers
Closely related to the barometer is the manometer, a device used to
measure the pressure of a gas.
Types of Manometers
1. Closed-end manometer
The gas pressure is equal to the difference in height (h) of the mercury
column in the two arms of the manometer

Closed end manometer

2. Open-end Manometer
The difference in mercury levels (h) between the two arms of the
manometer gives the difference between barometric pressure and the gas
pressure
Three Possible Relationships
1. Heights of mercury in both columns are equal if gas pressure
and atmospheric pressure are equal. Pgas = Pbar
2. Gas pressure is greater than the barometric pressure.
P > 0 Pgas = Pbar + h
3. Gas pressure is less than the barometric pressure.
P < 0 Pgas = Pbar - h

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The Gas Laws

There are four variables required to describe a gas:

Amount of substance: moles
Volume of substance: volume
Pressures of substance: pressure
Temperature of substance: temperature
The gas laws will hold two of the variables constant and see how the other
two vary

1. Boyles Law (The Volume - pressure relationship):

The Volume of fixed quantity of gas is inversely proportional to its
pressure.

1
V
p
constant
V
P
PV constant
P1V1 = P2V2

Processes that occur at constant temperature are said to be isothermal.

These pressure-volume data are often displayed on a plot of P versus V.

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Example 2.1
An ideal gas is enclosed in a Boyle's-law apparatus. Its volume is 247
ml at a pressure of 625 mmHg. If the pressure is increased to 825
mmHg, what will be the new volume occupied by the gas if the
temperature is held constant?
Solution
P V
Method 1: According to Boyle's law, P1V1 = P2V2 V 1 1
2 p
2
625 mmHgX247ml
V 187 ml
2 825 mmHg
Method 2: The pressure of the gas increases from 625 to 825
mmHg, or in other words, by a factor 825/625 because volume and
pressure are inversely proportional, the volume must decrease by a
factor of 625/825 Defining V1 and V2 as in Method 1 above, we can write
V2= V1 X (ratio of pressures)
625 mmHg
V 247 x 187 ml
2 825 mmHg

Example 2.2
Suppose 4.63 liters of an ideal gas at 1.23 atm is expanded at constant
temperature until the pressure is 4.14 x 10-2 atm. What is the final volume
of the gas?

Physical Chemistry First Year First semester Page 16

Solution
P1V1= P2V2
P1 V1
V2
p2
1.23 atm X 4.63L
V2 138 liters
4.14 x 10-2 atm

Example 2.3
Suppose 10.9 ml of an ideal gas at 765 mmHg is expanded at constant
temperature until its volume is 38.1 ml. What is the final pressure?

Solution
P1 V1
P1V1 = P2V2 or P2
V2
765 mmHgX 10.9 ml
P2 219 mmHg
38.1 ml
Method 2: The volume increases by a factor of 38.1/10.9. Because we know
that the pressure and volume are inversely proportional, we predict that
the pressure will decrease, and by a factor of 10.9/38. 1.
10.9 ml
P2 765 mmHg 219 mmHg
38.1 ml
(Note that 10.9/38. 1 is a fraction less than 1.)

2. Charles Law (The Temperature-Volume Relationship):

The volume of a fixed quantity of gas at constant pressure
increase as the temperature increases

V1 V2
V T or V1T2 = V2T1
T1 T2
V = a (t + 273) (at constant P, n)

Physical Chemistry First Year First semester Page 17

Where V is the volume of the gas, t is the; Celsius temperature, and a
is the slope of the straight line. Since the temperature on the Celsius scale
is related to that on the Kelvin scale by
T (Kelvin) = T (degrees by Celsius +273) we can write
V = a T (at constant P, n)

Example 2.4
A 4.50-L sample of gas is warmed at constant pressure from 300 K
to 350 K. What will its final volume be?
Given: V1 = 4.50 L, T1 = 300. K, T2 = 350. K
V1 V2
Equation: or V1T2 = V2T1
T1 T2
(4.50 L)(350. K) = V2 (300. K) V2 = 5.25 L

Example 2.5
An ideal gas occupies a volume of 1.28 liters at 25 C. If the temperature is
raised to 50 C, what is the new volume of the gas if the pressure remains
constant?

Physical Chemistry First Year First semester Page 18

 Solution
V1 V2 T2 V1
Solving for V2 V2
T1 T2 T1
The absolute temperatures are T1= 25 + 273 = 298 K and T2 = 50
+ 273 = 323 K. Thus, we have
(1.28 liters)(323K)
V2 1.39 L
298 K

3. Gay-Lussacs Law:
The pressure of a sample of gas is directly proportional to the
absolute temperature when volume remains constant

P1 P2
Or P1T2 = P2T1
T1 T2
The amount of gas and its volume are the same in either case, but if the
gas in the ice bath (0 C) exerts a pressure of 1 atm, the gas in the boiling-
water bath (100 C) exerts a pressure of 1.37 atm. The frequency and the
force of the molecular collisions with the container walls are greater at the
higher temperature.

Physical Chemistry First Year First semester Page 19

 4. Combined gas law
Pressure and volume are inversely proportional to each other and
directly proportional to temperature.

P1 V1 P2 V2
or P1V1T2 = P2V2T1
T1 T2

Example 2.6
Suppose 2.65 liters of an ideal gas at 25 C and 1 .00 atm is simultaneously
warmed and compressed until the final temperature is 75 C and the final
pressure is 2.00 atm. What is the final volume?
P1 V1 P2 V2
Solution: From combined gas law
T1 T2
Solving the above equation for V2 we have
T2P1 V1 1.00 atom x 2.65 liters x 348 K
V2 1.55 liters
P2T1 2.00 atm x 298 K

Example 2.7
A sample of gas is pumped from a 12.0 L vessel at 27C and 760 Torr
pressure to a 3.5-L vessel at 52C. What is the final pressure?
Given:
P1 = 760 Torr , V1 = 12.0 L, V2 = 3.5 L, T1 = 300 K and T2 = 325 K
Equation: P1 V1 P2 V2 or P1V1T2 = P2V2T1
T1 T2
(760 Torr)(12.0 L)(325 K) = ( P2)(3.5 L)(300 K)
P2 = 2.8 x 10 Torr

5. Avogadros Law (The Quantity-Volume Relationship):

At constant temperature and pressure the volume of a sample of gas is
proportional to the number of molecules (or the number of moles) in the
sample
V = c. n

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 6. The ideal gas equation
Combine the gas laws (Boyle, Charles, and Avogadro) yields a new
law or equation.
Ideal gas equation:
PV = nRT

R = gas constant = 0.08206 L.atm/mol-K

P = pressure (atm) V = volume (L)
n = moles T = temperature (K)

Gas that obeys this equation is said to be an ideal gas (or

perfect gas).
No gas exactly follows the ideal gas law, although many gases
come very close at low pressure and/or high temperatures.
Ideal gas constant, R, is
PV
R
nT
PV 1 atm x 22.4 L
R = 0.082058Latm/molK
nT 1 mol x 273.15K
R = 0.0821 liter atm K -1mol-1

Example 2.8
Suppose 0.176 mol of an ideal gas occupies 8.64 liters at a pressure of
0.432 atm. What is the temperature of the gas in degrees Celsius?
Solution PV = nRT
(0.432 atm)(8.64 liters)
258 K
(0.176 mol)(0.0821liter atm K -1mol-1 )
To
degrees Celsius we need only subtract 273 from the above result:
=258 - 273 = -15OC

Physical Chemistry First Year First semester Page 21

Example 2.9
Suppose 5.00 g of oxygen gas, O2, at 35 C is enclosed in a
container having a capacity of 6.00 liters. Assuming ideal-gas
behavior, calculate the pressure of the oxygen in millimeters of
mercury. (Atomic weight: 0 = 16.0)

Solution
One mole of O2 weighs 2(16.0) = 32.0 g.
5.00 g of O2 is, therefore, 5.00 g/32.0 g mol-1, or 0.156 mol.
35 C is 35 + 273 = 308 K
PV = nRT
(0.156mol)(0.0821 liter atm K - I mol - 1)( 308 K)
p 0.659atm
6.00 liters
760 mmHg
0.659 atm 500 mm Hg
1 atm

Molar volume of an ideal gas at STP

Using the ideal-gas law we can calculate what volume would be occupied
by 1 mol of an ideal gas at any temperature and pressure. A reference
condition which is commonly used for describing gas properties is 0C
(273.15 K) and 1.0000 atm (760.00 mmHg), called standard temperature
and pressure, or more briefly, STP.
The volume occupied by one mole, or molar volume, of an ideal gas at
STP is
nRT
V
P
(1.0000 mol)(0.082057 liter atm K -I mol-1 )( 273.15 K)

1.0000 atm
22.414 liters

Physical Chemistry First Year First semester Page 22

 7. Daltons Law (Gas Mixtures and Partial Pressures):
In a gas mixture the total pressure is given by the sum of partial
pressure of each component
Pt= P1 + P2 + P3.

- The pressure due to an individual gas is called a partial pressure.

Gas 1 P1 = n1RT P1 = n1RT

V (1)
n2RT
Gas 2 P1 = n2RT P2 =
V (2)
Gas 3 P1 = n3RT P3 = n3RT
V (3)
n 1RT n 2RT n 3RT
Pt =
V V V
RT RT
= (n1 + n2 + n3) = nt
V V (4)
By dividing equations (1), (2), and (3) by (4) we get,

n1 P1 n1
P1 Pt
n t Pt and nt (5)
n 2 P2 n2
P2 Pt
n t Pt and nt (6)
Where
n1 P1
= X1 = mole fraction of the first gas
n t Pt
n 2 P2
= X2 = mole fraction of the second gas
n t Pt

Physical Chemistry First Year First semester Page 23

Note that the sum of all mole fractions in a system will be equal to
unity X1+ X2+ X3 = 1

Therefore, the final equation of Dalton's law of partial pressures

becomes:
P1 = Pt X1 and P2 = Pt X2

Example 2.10
A gaseous mixture made from 6.00 g O2 and 9.00 g CH4 is placed in
a 15.0 L vessel at 0C. What is the partial pressure of each gas, and
what is the total pressure in the vessel?
1 mol O2
Step 1: nO2 = 6.00 g O2 x = 0.188 mol O2
32 g O2
1 mol CH4
nCH4 = 9.00 g CH4 x = 0.563 mol CH4
16 g CH4
Step 2: Calculate pressure exerted by each
nRT
PO2 =
V
(0.188mol O2)(0.0821L - atm/mol - K)(273K)
= = 0.281 atm
15.0 L
(0.563mol)(0.0821 L - atm/mol - K)(273K)
PCH4= =0.841 atm
15.0 L
Step 3: Add pressures
Ptotal = PO2 + PCH4 = 0.281 atm + 0.841 atm
Ptotal = 1.122 atm

Physical Chemistry First Year First semester Page 24

 8. Grahams Law (Molecular Effusion and Diffusion):
The rate of effusion of a gas is inversely proportional to the
squre root of its molecular mass

Effusion The escape of gas

through a small opening.
Diffusion The spreading of one
substance through another.

m m
d so V
V d
m
Ideal Gas Equation: PV = nRT and n
M
Substituting m mRT
p
d M
PM
m cancels out d
RT

Example 2.11
The rate of effusion of an unknown gas (X) through a pinhole is found
to be only 0.279 times the rate of effusion of hydrogen (H2) gas through
the same pinhole, if both gases are at STP. What is the molecular
weight of the unknown gas? (Atomic weight, H = 1.01.)

Solution

Physical Chemistry First Year First semester Page 25


Mx= 26.0

9. Deviations from Ideal Behavior

To describe the behavior of a gas, we must first describe what a

gas is:
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.
Energy can be transferred between molecules, but total kinetic
energy is constant at constant temperature.
Average kinetic energy of molecules is proportional to
temperature.

Ideal gas on obeys the gas law PV =

Gases may be
constant (at constant T)

Real gas Deviate (not obey to gas law PV

Constant)

Real gas deviate from ideal gases when (T is very low and P
is very high).
The dependence of real gases from ideal behavior can be
account by two factors which were ignored by the kinetic
theory.
1. Real gases posses attractive forces between molecules.
2. Every molecule in a real has a real volume.

Physical Chemistry First Year First semester Page 26

 There are 2 correction factors should be taken into
consideration:

1. Volume of gas molecules is not negligible:

True volume (Real) = V container non copressiable volume (b)
= V- b for 1 mole
Actual volume = V nb ( for n mole)

1. There is a force of attraction between the molecules of

gases: (pressure)
Actual pressure = measured pressure + pressure due to attraction
force.
a an 2
p 2 1 mole p 2 n moles
V V
1 1 1 a
N.B bulk surface force . 2 2
V V V V
Van der Walls Equation
For ideal gases PV = n RT but in case of real gases
PV nRT
When introduce actual volume & actual pressure
P ideal . V effective = n RT
The Van der Waal's equation is represented as:
a
p (V b) RT
V2 for 1 mole

Physical Chemistry First Year First semester Page 27

 an2
p 2 (V nb) nRT
V for n mole

The last equation is known as Van der Waal's equation where a, b

are Van Waals constants depend on the nature of the gas.

Note that:
According to Van der Waal's, the persevere of a real gas will be
lower than that of an ideal gas because attraction to neighboring
molecules tends to decrease the impact of a real molecule that it
makes with the wall of the container, this can be expressed.
an 2
P real = P Ideal - 2
V
Van der Waals constants for some gases
Gas a (L2.atm/mol2) b (L/mol)
CO2 3.658 0.04286
Ethane C2H6 5.570 0.06499
Methane CH4 2.25 0.0428
Helium He 0.0346 0.0238
Hydrogen H2 0.2453 0.02651
Oxygen O2 1.382 0.03186
Sulfur dioxide SO2 6.865 0.05679

Physical Chemistry First Year First semester Page 28

Example 2.12
Calculate the pressure exerted by 10.0 g of methane, CH4, when enclosed
in a 1.00-liter container at 25 C by using (a) the ideal-gas law and (b) the
van der Waals equation. (Using the above table)

Solution
The molecular weight of CH4 is 16.0; so n, the number of moles of
methane, is 10.0 g/16.0 g mol-1, or 0.625 mol.

(a) Considering the gas to be ideal and solving for P, we obtain

nRT (0.625mol)(0.0821 liter atm K -1 mol 1 )(298K)
P
V 1.00 liter
15.3 atm

(b) Treating the gas as a Van der Waals gas and solving for P,
we have nRT n2a
P
V nb V2
(0.625 mol)(0.0821 liter atm K -1 mol 1 )(298K)
P
1.00 liter - (0.625 mol) ( 0.248 liter mol -1 )
(0.625 mol) 2 (2.25 liters 2 atm mol 2 )

(1.00 liter) 2
14.8atm

Physical Chemistry First Year First semester Page 29