Unit Three -9- Chapter Six

Gas Laws
Brownian motion:

When a candle smoke is observed by microscope, we can see that the smoke

particles move randomly.

An English botanist (Brown) fined that the molecules of any gas in case of

continually and randomly motion.

Gas state:

Gas molecules in case of random translatory motion.

Liquid state:

Liquid molecules in case of random translatory motion, and random

vibratory motion.

Solid state:

Solid molecules in case of random vibratory motion.

Brownian motion explanation:

• Any gas consists of molecules.

• The molecules in case of motion randomly.

• Some of the molecules are faster than the other.

• During the motion the molecules collide each other and collide the walls

of the container.

• The number of collation at one side of the molecule is not equal to that at

the other side, which makes the molecule to change its direction.

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Unit Three -10- Chapter Six

Experiment:

Explain an experiment as evidence of the existence of intermolecular

distances, and random motion of gas molecules:

1. Fill a graduated cylinder

hydrogen chloride gas.

2. FILL another cylinder

with ammonia gas, and

placed it upside down

on the first cylinder.

3. Notice that white cloud of ammonium chloride is formed, then it grows and

diffuses until it occupies all the space within the two cylinders.

Explanation:

1. Hydrogen chloride gas molecules in spite of their higher density diffuse

upwards, through spaces separating ammonia gas molecules, where they

combine together forming ammonium chloride molecules. Which diffuse to

fill the upper cylinder.

2. Ammonia gas molecules in spite of their lower density diffuse downwards

through spaces separating hydrogen chloride gas molecules, where they

combine forming ammonium chloride molecules, which diffuse to fill the

lower cylinder.

3. We can conclude that there are large spacing separating the gas molecules.

The Gas Laws:

The volume of any gas affected by the temperature and the pressure;

therefore, there are three laws to explain the gases behavior.

• The relation between volume and pressure at constant temperature

(Boyle's law).
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Unit Three -11- Chapter Six

• The relation between volume and temperature at constant pressure

(Charles’s law).

• The relation between pressure and temperature at constant volume

(Pressure law).

Boyle's law:

Boyle's Experiment:

• Connect a burette to a glass reservoir with a rubber tube.

• But a suitable amount of mercury

in the rubber tube.

• The tap (A) is opened and the

reservoir (B) is raised until the

mercury level in burette A is about

half full, taking into account that

the mercury levels are the same in

both sides.

• The tap (A) is then closed, the

volume of the enclosed air is

measured, let it be (Vol)1 its pressure is also measurd, let it be P1, which

equals the atmospheric pressure Pa which may be determined using a

barometer.

• The reservoir (B) is then raised a few centimeters and the volume of the

enclosed air is measured (Vol)2 the difference between the two levels of

mercury in both sides (h) is determined. In this case, the pressure of the

enclosed air is P2 = Pa + h

• Repeat the previous step by raising the reservoir (B) another suitable

distance and measure (Vol)3 and P3 in the same manner.

Summary 2008/2009
Unit Three -12- Chapter Six

• The reservoir (B) is then lowered until the mercury level in (B) becomes

lower than its level in (A) by a few centimeters. Then the volume of the

enclosed air is measured (Vol)4 and its pressure P4 is determined P4 = Pa –

h, where h is the difference between the two levels of mercury in both

sides.

• The previous step is repeated once more by lowering (b) another suitable

distance< then (vol)% and p% are measured in the same manner.

• Plot the volume of the enclosed air (Vol) and the reciprocal pressure, we

obtain a straight line, thus we can conclude that volume is inversely

proportional to the pressure, at constant temperature.

Graphical relations:

• Draw a graph between V and P.

V V
1
V∝
P

1/P
P

• From the graph, we can conclude the relation between pressure and

volume, where: or VP = constant.

Boyle's law statement:

• The volume of fixed mass of gas is inversely proportional to the pressure,

provided that the temperature remains constant.

• At a constant temperature, the product PV of any given mass of a gas is

constant.

Summary 2008/2009
Unit Three -13- Chapter Six

Charles's law:

Explain an experiment to show that equal volume of different gases at

constant pressure expand by the same amount:

• Take two flasks of exactly

equal volume, each fitted with

a cork through which a tube

bent 90 is inserted in each tube,

there is a thread of mercury of

length 2 or 3 cm, fill one of the flasks with oxygen and the other with

carbon dioxide or air. Submerge the two flasks in a vessel filled with

water as shown in the figure.

• Pour hot water into the vessel and notice the distance moved by the

mercury thread in both tubes, you will find that these distances are equal,

this indicates that equal volumes of different gases expand equally when

heated through the same temperature rise. In other word they have the

same volume expansion coefficient.

• We will find that: The same volumes of different gases, at constant

pressure, expand by the same values.

VαT

V1 T1
=
V2 T2
V V

T
1/T

Summary 2008/2009
Unit Three -14- Chapter Six

Volume expansion coefficient of a gas at constant pressure:

It is the increase in unit volume at constant pressure per unit volume at 0°C

for 1°C rise of temperature.

Explain an experiment to investigate the relation between the gas

volume and its temperature at constant pressure:

1. The apparatus is consists of a capillary glass tube 30 cm long and bout 1 mm

diameter with one end closed. The tube contains a short pellet of mercury

enclosing an amount of air inside it whose length is measured by a ruler stand,

the apparatus is equipped

with a thermometer inside a

glass envelope.

2. The glass envelope is packed

with crushed ice and water.

It is then left until the air

inside the glass tube has

fully acquired the

temperature of melting ice.

3. the length of the enclosed air is then measured. And since the tube has a

uniform cross section the length of the enclosed air is taken as being

proportional to its volume.

4. the ice and water are removed from the envelope and steam is passed through

the top and out at the bottom for several minutes to be sure that the

temperature of air becomes 100 C, then the length of the enclosed air is

measured, it is taken as a measure of its volume.

5. a relation between volume and temperature plotted. We see that such a relation

is a straight line, which if extended will intersect the abscissa at – 273C.

Summary 2008/2009
Unit Three -15- Chapter Six

6. The volume coefficient of air at constant pressure α is then determined using

V100 − V0
the relation ∝=
100V0
Precautions:

1. The tube must be a narrow tube to notice the increase in the gas volume.

2. The tube must has uniform cross sectional area to make the length of the

gas indicator to the volume without any effect of the cross sectional area.

Generally:
∆V
∝=
V ∆t
∆V =∝ V ∆t

The value of αv is 1/273 for all gases.

∆V = αv V0 ∆t

V - V0 = αv V0 ∆t

V = V0 + αv V0 ∆t

V = V0 (1 + αv ∆t)

In case of starting by the same volume:

V1 1+ ∝ ∆t1
=
V2 1+ ∝ ∆t 2

Charles's law statement:

• The volume of a given mass of gas, kept at constant pressure, expands by

1/273 of its volume at 0ºC per each degree Kelvin rise in temperature.

• At a constant pressure, the volume of any given mass of a gas is directly

proportional to the temperature in Kelvin.

Summary 2008/2009
Unit Three -16- Chapter Six

Pressure law:

Explain an experiment to investigate how pressure of a gas depends on

temperature:

• The gas under test is confined in a flask by mercury in a U tube. The

flask is fitted with a cork; the surface of mercury in the two branches (A)

and (B) have the same level at x, y, thus, the pressure of the enclosed air

is atmospheric. We then determine the temperature of air let it t1 C.

• Submerge the flask in a vessel containing warm water at t2 C. you will

notice that the level of mercury decreases in branch A, while it rises in

branch B.

• We pour mercury in the funnel C, until the level of mercury in branch A

returns to the mark x then the volume of the enclosed air in the flask at t2

C is equal to the volume at t1 C.

• We notice that the surface of mercury in branch B exceeds that in branch

A by an amount "h" this means that the pressure of the enclosed air has

increased as a result of the temperature rise from t 1 to t2 by an amount

equal h cm Hg.

• Repeating this experiment several times for different gases and

measuring the amount f increases of gas pressure at constant volume for

Summary 2008/2009
Unit Three -17- Chapter Six

the same rise in temperature, we find: at constant volume, the pressure of

a given mass of gas increases by increasing temperature, and at constant

volume, equal pressure of gases increases equally, when heated through

the same range of temperature.

• From the previous experiment, we can conclude that the relation between

pressure and temperature at a constant volume is directly proportional.

PαT
P1 T1
=
P2 T2

P P

T
1/T
Jolly's Experiment:

1. It consists of a glass bulb (A), the

bulb is joined to a capillary tube (B)

bent in the form of two right angles,

the bulb and the tube are mounted

on a vertical ruler attached to a

board which is fixed on a horizontal

base provided with 3 leveling

screws. The capillary tube (B) is

connected to a mercury reservoir (C)

by means of a rubber tube.

2. Determine the atmospheric pressure (Pa) using a barometer.

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Unit Three -18- Chapter Six

3. Pour mercury in (A) to 1/7 of its volume to compensate for the increase in its

volume when heated, so that the volume of the remaining part is still constant.

(The volume expansion coefficient of mercury is seven times the volume

expansion coefficient of glass).

4. Submerge reservoir (A) in a beaker filled with water and pour mercury in the

free end (C) until it rises in the other branch to mark (X).

5. Heat water in the vessel to the boiling point and wait until the temperature

settles, and the mercury level in the branch connected to the reservoir stops

decreasing.

6. Move the free end (C) upwards until the mercury level in the other branch

rises to the same mark X. then measure the difference in height between the

mercury levels in the two branches (h) from this determine the pressure of the

enclosed air P, where P = Pa + h

7. Move the branch (C) downwards and stop heating, then let the reservoir cool

down to nearly 90 C, then move the branch (C) upwards until the mercury

level in the branch connected to the reservoir rises to mark X. then determine

the temperature and the difference in height between the mercury levels in

both branches, from this we calculate the pressure of the enclosed air in this

case.

8. Repeat at different temperature and determine the pressure of the enclosed gas

in each case.

9. Plot the relation between pressure and temperature. We find that the relation is

a straight line.

10. calculate the pressure coefficient of gas at constant volume from the equation:

β= ∆P
P ∆t

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Unit Three -19- Chapter Six

Generally:

β= ∆P
P ∆t
∆P = βP ∆t

The value of β is 1/273 for all gases.

∆P = β P0 ∆t

P - P0 = β P0 ∆t

P = P0 + β P0 ∆t

P = P0 (1 + β ∆t)

In case of starting by the same pressure:

P1 1 + β∆t1
=
P2 1 + β∆t 2

Pressure law statement:

• The pressure of a given mass of any gas, kept at constant pressure,

changes by 1/273 of its pressure at 0ºC per every 1ºC change of

temperature.

• At a constant volume, the pressure of any given mass of a gas is directly

proportional to the temperature in Kelvin.

The absolute zero (Zero Kelvin):

• By drawing of a graph between volume and temperature in Celsius, we

can find that the gas has a certain value at 0°C, and the relation between

volume and temperature is directly proportional.

• If we make an extension to the relation between volume and temperature,

the line will intersect the X axis at a point = -273°C

• At this temperature the volume of gas can be considered as zero.

• This temperature considered as the 0°K

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Unit Three -20- Chapter Six

• Therefore: K = C + 273.

• The same result can be reached by using of the graph between pressure

and temperature.

V P

-273 t -273 t
General gas law:
1
• From Boyle's law: V ∝ (T = cons tan t )
P

• From Charles's law: V ∝ T ( P = cons tan t )

T
• Therefore: V ∝
P
T
• V = const
P
PV
= Const
T
PV P′V ′
=
T T′

N.B.:

• T: must be in Kelvin where K = C + 273

• One mole of any gas has volume of 22.4 liter, at NPT

• Liter = 10-3 m3

• The constant value (PV/T) is called general gas constant, its unit is J/K

and has value of 8.31

PV
• For one mole of any gas = R or PV = RT
T

• For any amount of gas PV = nRT, where n is the number of moles.

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Unit Three -21- Chapter Six

P1V1 P2V2 PmixVmix

• When two gases mixed in one container: + =
T1 T2 Tmix

• When two gases mixed and each remains in its container:

′ ′ ′ ′
P1V1 P2V2 P1 V1 P2 V2
+ = +
T1 T2 ′ ′
T1 T2
PV P′V ′ PM P ′M ′
• The relation = can be replaced with =
T T′ Tρ T ′ρ ′
P P′
• For a constant mass the relation becomes =
Tρ T ′ρ ′
P P′ PV P ′V ′
• Also this relation = can be replaced with =
Tρ T ′ρ ′ TM T ′M ′

• For a constant volume of gas with change of mass like the case in which
P P′
some gas escape from the container; the relation becomes =
TM T ′M ′

Summary 2008/2009