Ideal gas laws

Gas Studies
 Boyle’s Law
 Charles’s Law
 Gaylusac’s Law
 The Combined Gas Law
 Avogadro’s Law
 Graham’s law of Diffusion
 Dalton’s Law of partial pressures
 Van der Waal’s Equation
 The Joule-Thomson Process
 Linde process for liquefaction of gases
 Claude process for liquefaction of gases
 Gas properties
 Gases Have Mass
 Gases Diffuse
 Gases Expand To Fill Containers
 Gases Exert Pressure
 Gases Are Compressible
 Pressure & Temperature Are
Dependent
 Gas variables
 VOLUME (V)
– UNITS OF VOLUME (L)
 AMOUNT (n)
– UNITS OF AMOUNT (MOLES)
 TEMPERATURE (T)
– UNITS OF TEMPERATURE (K)
 PRESSURE (P)
– UNITS OF PRESSURE (mmHg)
– UNITS OF PRESSURE (kPa)
– UNITS OF PRESSURE (atm)
– UNITS OF PRESSURE (torr)
 VOLUME (V)

• UNITS OF VOLUME (L)

• Cubic meter (m3) 1m3 = 1000 L
• Cubic Centimeter 1 Cm3 = 1 ml = 10-3 L
 AMOUNT (n)

• UNITS OF AMOUNT (MOLES)

mass (gr)
No. of moles  mole
M Wt
mass (mg)
No. of mmoles  mmole
M Wt

• mmole = 10-3 mole

 TEMPERATURE (T)

• UNITS OF TEMPERATURE (K)

• TEMPERATURE (K) = t 0C + 273
• degree Fahrenheit°F
• T[°F] = T[K] × 1.8 − 459.67
• T[°F] = 1.8 × T[°C] + 32
 Pressure
F
• Pressure is defined as force divided by the area. P
A
SI unit: Pascal (Pa)
• 1 Pa = 1 N/m2 = 1 Kg/m.s2
Conventional units
• 1 atm = 101325 Pa = 101.325 kPa
• 1 bar = 105 Pa = 100 kPa
• 1 atm = 76 cmHg = 760 mmHg = 760 Torr
• 1 atm = 14.7 Ib/inch2
 Boyle’s Law
•Boyle’s Law states that at constant temperature the volume of a
fixed amount of gas is inversely proportional to its pressure.

 1  1 
P 1 P 2
 V 1   V 2  at constant T & n
K K
P1  P2 
V1 V2
P1 V1  K P2 V2  K
P1 V1  P2 V2
Boyle’s Law
[P1V1 = P2V2] at constant T & n
 Example:
• Sulfur dioxide (SO2), a gas, that plays a
central role in the formation of acid rain, is
found in the exhaust of automobiles and
power plants. Consider a 1.53 L sample of
gaseous SO2 at a pressure of 5.6 x 103 Pa.
If the pressure is changed to 1.5 x 104 Pa at
a constant temperature, what will be the
new volume of the gas?
 Solution:
P1V1= P2V2

P1= 5.6 x 103 Pa P2= 1.5 x 104 Pa

V1= 1.53 L V2= ?
Rearrange the formula to isolate V2.
P1V1 = (5.6X 103 Pa)(1.53 L) = O.57 L
P2 (1.5 X 104 Pa)
 Jacques Charles
In the century following
Boyle, a French physicist,
Jacques Charles (1746-
1823), was the first
person to fill a balloon
with hydrogen gas and
who made the first solo
balloon flight.
 Charles’s Law
• Charles’s Law states that at constant pressure the
volume of a fixed amount of gas is directly
proportional to its absolute temperature.
• V1αT1 , V2αT2
• V1=T1 K , V2=T2 K
• V1/T1= K , V2/T2= K

• V1/T1= V2/T2

 V1 V2 
 T1  
T2  at constant P & n
 Volume vs. Temperature:
Charles’ Law
• Notice the linear relationship. This relationship between
temperature and volume describes a “direct relationship”.
This means when temperature increases, so does the
volume.
 Example:
• A sample of a gas at 15°C and 1 atm has a
volume of 2.58 L. What volume will the
gas occupy at 38°C and 1 atm?

• (NOTE: The pressure did not change. So

you do not need to worry about it!)
 Solution:
• V1 = V2 Don’t forget to convert °C to K
T1 T2

V1= 2.58L V2=?

T1 = 15°C=288K T2 = 38°C=311K
Rearrange to solve for V2.
V1T2 = (2.58L)(311K) = 2.79 L
T1 (288K)
 Gaylusac’s Law
• Gaylusac’s Law states that at constant
volume the pressure of a fixed amount of
gas is directly proportional to its absolute
temperature.

P1 P2

T1 T2
 The Combined Gas Law
• The combined gas law was derived from
Boyle’s and Charles’s work. A direct
relationship was observed. As temperature
increased, volume increased. As volume
increased pressure increased. This resulted
in a combined formula to calculate changes
observed in a gas due to changes in either
temperature, pressure or volume.
Combined Gas Law Equation
P1V1  P2V2 Boyle’s law
V1 V 2
 Charl’s law
T1 T 2
P1 P 2
 Gaylusac’s law
T1 T 2
2 2
 P1V 1   P 2V 2 
   
 T1   T 2 
P1V1 P2V2

T1 T2
 Combined Gas Law Equation
• By combining the equation for Boyle’s Law
and Charles’s Law. We derive the Combined
Gas Law Equation where:

P1V1 P2V2

T1 T2
 Example:
• A sample of a gas at 15°C and 2.0 atm has a
volume of 2 mL. What volume will the gas
occupy at 38°C and 1 atm?
 Solution
P1V1 = P2 V2 Don’t forget to convert Temperatures!
T1 T2
P1= 2 atm P2= 1 atm
V1=2 mL V2=?
T1=15°C=288K T2=38°C=311K
Rearrange to solve for V2!
V2= P1V1T2 = (2 atm)(2 mL)(311K) = 4.32 mL
T1P2 (288K)(1 atm)
 Example problem
A GAS WITH A VOLUME OF 4.0L AT STP.
WHAT IS ITS VOLUME AT 2.0 ATM AND AT
30°C?

P1  1atm P2 2.0 atm

V1  4.0 L V2  ?
T1  273K T2  30°C + 273
= 303K
P1V1 P2V2
=
T1 T2

2.22L = V2
 Avogadro’s Law
When a gas is at constant T and P, the V is
directly proportional to the number of moles (n)
of gas
V1 V2

n1 n2

initial final
 Summary – The Gas Laws
• Boyle’s law
V 1 at constant T, n
• Charles’s law
P
V T at constant P, n

• Avogadro’s hypothesis
V n at constant T, P

• Combining them all into one proportionality:

V nT
P
• To express this as an equality, we use a constant:
nT
V  constant 
P
PV  nRT
(R WHERE R IS THE UNIVERSAL GAS CONSTANT)
The Ideal Gas Law equation
 Ideal gas law
 IF
WE COMBINE ALL OF THE
LAWS TOGETHER INCLUDING
AVOGADRO’S LAW MENTIONED
EARLIER WE GET:

PV WHERE R IS THE
=R UNIVERSAL GAS
nT CONSTANT
NORMALLY
WRITTEN AS PV=nRT
 Ideal gas constant(R)
R IS A CONSTANT THAT
CONNECTS THE 4 VARIABLES
 R IS DEPENDENT ON THE UNITS
OF THE VARIABLES FOR P, V, & T
– TEMP IS ALWAYS IN KELVIN
– VOLUME IS IN LITERS
– PRESSURE IS IN EITHER atm OR
mmHg OR kPa
  BECAUSE OF THE DIFFERENT
PRESSURE UNITS THERE ARE 2
POSSIBILITIES FOR OUR R
– IF PRESSURE IS L•atm
GIVEN IN atm, V in L R=0.0821
mol•K
– IF PRESSURE IS L•kPa
GIVEN IN kPa, V in L R=8.314
mol•K
– IF PRESSURE IS GIVEN R=8.314 m 3•Pa

IN Pa, V in m3 mol•K

– IF PRESSURE IS J
GIVEN IN Pa, V in m3 R=8.314
mol•K
R = 8.314472 J·mol−1·K−1
= 8.314472 m3·Pa·K−1·mol−1
= 8.314472 kPa·L·mol-1·K-1
= 0.08205746 L·atm·K−1·mol−1
= 62.36367 L·mmHg·K−1·mol−1
= 10.73159 ft3·psi·°R−1·lb-mol−1
= 53.34 ft·lbf·°R−1·lbm−1 (for air)
 Using Ideal gas law
Ex #1: WHAT VOL DOES 9.45g
OF C2H2 OCCUPY AT STP?

R  L•atm
P 1atm 0.0821
mol•K
V ? T  273K
9.45g
n =0.3635 mol
26g
 PV = nRT
(1.0atm) (V) =
(0.0821L•atm ) (273K)
(0.3635mol) mol•K

(1.0atm)(V) =(8.147L•atm)
V = 8.15L
 Using Ideal gas law
Ex #2:
A CAMPING STOVE PROPANE TANK HOLDS
3000g OF C3H8.
HOW LARGE A CONTAINER WOULD BE
NEEDED TO HOLD THE SAME AMOUNT OF
PROPANE AS A GAS AT 25°C AND A
PRESSURE OF 303kPa?
 Using Ideal gas law
L•kPa
P  303kPa R  8.314
mol•K
V ? T  298K
3000g
n =68.2 mol
44g

PV = nRT
(303kPa) (V)=
(68.2mol) (8.314 L•kPa ) (298K)
mol•K

(303kPa) (V) = (168,970.4L•kPa)

V = 557.7L
 PV = nRT
mass gr mass gr
n , 
M Wt V
PV  nRT , PV  mass gr
MWt
RT
PM Wt  mass gr
V
RT
PM Wt  RT MWt is molar mass,  is density

PMwt = pRT
 Diffusion
Thomas Graham proposed a Law
(1883) to summarize experimental
observations on diffusion

Rate of Diffusion  1/√M

Relative rates of
diffusion

r1 M2

r2 M1
 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 (partial
pressure)
PT=P1+P2+P3+….Pn
Mole fractions: xi = ni/n
Pi ni RT / V n
  i
PT nT RT / V nT
 ni 
Pi    PT  xi PT
 nT 
Q: If dry air is composed of N2, O2, Ar at sea level in
mass percent of 75.5: 23.2: 1.3. What is partial pressure
for each when total pressure is 1.0 bar (100 kPa)?
 Density of a Gas
Density (p) = mass (m)
Volume (V)

• We can solve for density in the Ideal Gas Law using

substitution:
PV = nRT
n = m/MWt
PV = mRT
MWt
p = m = P(MWt)
V RT
9-
 Daltons’ Law of Partial Pressures
Partial Pressure
Pressure each gas in a mixture would exert
if it were the only gas in the container
Dalton's Law of Partial Pressures
The total pressure exerted by a gas mixture
is the sum of the partial pressures of the
gases in that mixture.
PT = P 1 + P2 + P3 + .....
 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 (partial
pressure)
PT=P1+P2+P3+….Pn
Mole fractions: xi = ni/n
Pi ni RT / V n
  i
PT nT RT / V nT
 ni 
Pi    PT  xi PT
 nT 
Q: If dry air is composed of N2, O2, Ar at sea level in
mass percent of 75.5: 23.2: 1.3. What is partial pressure
for each when total pressure is 1.0 bar (100 kPa)?
 Gas mixtures
Mass fractions: xi = mi/mt

P M Wt  RT

MWtaverage    X MWt  i   Xi MWti

 XaMWt a  XbMWtb  ......
note :  Xi  ( Xa  Xb  ...)  1
P Mwt = pRT
Pa = XaPT, Pb = XbPT
 Gases in the Air
The % of gases in air Partial pressure (STP)
78.08% N2 593.4 mmHg
20.95% O2 159.2 mmHg
0.94% Ar 7.1 mmHg
0.03% CO2 0.2 mmHg
PAIR = PN2 + PO2 + PAr + PCO = 760 mmHg
Total Pressure = 760 mm Hg
 Learning Check

A.If the atmospheric pressure today is 745 mm Hg,

what is the partial pressure (mm Hg) of O2 in the
air?
1) 35.6 2) 156 3) 760

B. At an atmospheric pressure of 714, what is the

partial pressure (mm Hg) N2 in the air?
1) 557 2) 9.14 3) 0.109
 Solution

A.If the atmospheric pressure today is 745 mm Hg,

what is the partial pressure (mm Hg) of O2 in the
air?
2) 156

B. At an atmospheric pressure of 714, what is the

partial pressure (mm Hg) N2 in the air?
1) 557
 Partial Pressures

The total pressure of a gas mixture depends

on the total number of gas particles, not on
the types of particles.
P = 1.00 atm P = 1.00 atm

0.5 mole O2
1 mole H2 + 0.3 mole He
+ 0.2 mole Ar
 Sheet
 1- A gaseous mixture composed of 8 gm He, 20 gm Ne and 80 gm
of Ar is confined in 22.4 liter container at 0oC. Calculate:
 i- The total pressure of the mixture.
 ii- The partial pressure of each gas.

 2- Calculate the value of the general gas constant R in L.atm/mole. K

at S.T.P.

 3- Calculate the molar mass of a gas of a density 1.2 gr/L at 27 oC

under one atmospheric pressure

 4- Calculate the pressure of 88 gm of CO2 gas at 27 oC in 5 liter

container.
 – suppose Ideal gas state.
 – suppose Real gas state
 ( a = 3.5 L2 atm / mol2 , b = 0.04 L / mol. )
 Real Gases
&
Van der Waal’s Equation
 Real Gases

• Unlike Ideal Gases, real molecules do

take up space and they do interact with
each other (especially polar molecules).
• We need to add correction factors to the
ideal gas law to account for these factors.
 Volume Correction
• The actual volume the molecules are
free to move in, is less because of
particle size.
• More molecules will have more
effect.
Corrected volume V’ = V - nb
• b is a constant that differs for each
gas. Larger molecules have a bigger
“b”.
 Pressure correction
• Because the molecules are
attracted to each other, the pressure
on the container will be less than
ideal.
• depends on the number of
molecules per liter.
• since two molecules interact, the
effect must be squared.
 •P’ = Pobserved + a (n/V) 2

 Adding the Pressure Correction

and Volume Correction to the
Ideal Gas Law, you have van der
Waal’s Equation.
 Insert van der Waal’s equation
 Van der Waal’s equation

For one mole n = 1

 2

 P  an v  nb   nRT For mole n = 1
 2 
 v 
 Where does it come from :
• a and b are determined by experiment
(they are given).
• Different for each gas.
• Bigger molecules have larger b.
• a depends on both size and polarity of
the molecule.
• once given, plug and chug.
The JOULE EXPERIMENT
To measure pT i.e. test U as a function of V for a real gas.

Joule detected no temperature

change i.e. q = 0.
 U 
pT   
 V T Any work done? NO, so w = 0.

Interpretation

DU = q + w = 0 (1st law).

U does not change with a change

in V, i.e. pT = 0.

This is not a very sensitive experiment

because water has a much higher Cp
than air.
 The problem in implementing the expansion engine
The Joule-Thomson for deep cooling (e.g., gas liquefaction): the engine
Process does not work well at low T (no good lubricants!)

Let’s consider case (b) - the process of expansion

through a cnstriction or porous plug. This is the so-
called throttling or Joule-Thomson process. The
JT effect is essentially irreversible (this is a
disadvantage), but it does not require moving
mechanical parts of the fridge at low T.

The JT process corresponds to an isenthalpic expansion:

H1  H 2   W  0 H1  H 2 U1  P1V1  U 2  P2V2
For an ideal gas, this process won’t result in any T change:

f f 2
H  U  PV  N k BT  N k BT  N k BT H = const means T = const
2 2 for an ideal gas

Thus, we cannot cool an ideal gas by going through the Joule-Thomson process!
(Recall a similar process – expansion of an ideal gas through a hole in vacuum).

Luckily, for real gases, the temperature does change in the Joule-Thomson process.
 Simple Expansion Refrigerator

Compressor Compression at T~ 300K and cooling

to T~ 300K by ejecting heat into the
Heat environment
ejection gas pre-cooling in a counter flow heat
exchanger
cooling to the lowest T in the expansion
engine, usually a low friction turbine
Heat heat extraction from the cooling load.
exchanger
The work extracted from a fixed mass of the
Expansion working gas by the expansion engine:
engine
 W  H1  H 2
For an ideal monatomic gas:
5 2 W
H N k BT T1  T2 
2 5 N kB

Cooling This process works for both ideal and real gases.
volume
 Compressor
(To 200 atm)

Unliquid gas Cooling coil

Heat exchanger
High pressure gas
Expansion valve
Low pressure gas

Liquid gas

Linde process for liquefaction of gases

 Claude process for liquefaction of gases

(1)
Compressor
(To 200 atm)
Heat exchanger
Expansion engine
(2)
High pressure gas
Unliquid gas Expansion valve
Low pressure gas

Liquid gas