Mercury barometer

A mercury barometer is used to measure atmospheric pressure by

determining the height of a mercury column supported in a sealed glass tube.

The downward pressure of the mercury in the column is exactly balanced

by the outside atmospheric pressure that presses down on the mercury in the
dish and pushes it up the column. 1
 Open-end manometer

The pressure in the

bulb is higher than
atmospheric, so the
The pressure in the mercury level is
bulb is lower than higher in the arm
atmospheric, so the open to the
mercury level is atmosphere.
higher in the arm
open to the bulb.

Open-end manometers for measuring

pressure in a gas-filled bulb
2
 Gas Pressure Units
Gas pressure is the collisions of randomly moving particles
with the walls of the container exert a force per unit area.

SI Units of pressure: atmosphere (atm)

Other units:
1 atm = 760 mm Hg = 760 torr (1 mm Hg = 1 torr)
1 atm = 101325 Pa = 101.3 kPa (1 Pa = 1 N/m2) 1 atm
= 1.01325 bar
1 atm = 29.921 in Hg
1 atm = 14.7 lb/in2
1 atm = psi
3
 The Gas Laws
The physical properties of any gas can be described
completely (more or less) by four variables:

The specific relationships among these four variables

are the gas laws, and a gas whose behavior follows
these laws exactly is called an ideal gas.

There are four key gas law equations that have been
empirically determined, which are combined into the
combined gas law and the ideal gas law.

4
 Boyle’s Law: Pressure and
Volume
Pressure–Volume Law:
• The volume of a fixed
amount of gas maintained
at constant temperature
is inversely proportional
to the gas pressure.

As the volume of the gas

decreases, the gas
particles have less room
to move around in, and
they collide more often (n, T constant)
with the walls of the
container, thus increasing
the pressure.
5
 Charles’ Law: Temperature
and
Temperature–Volume
Volume
Law:
• The volume of a fixed
amount of gas at constant
pressure is directly
proportional to the Kelvin
temperature of the gas
(not the Celsius temp!)
• If the absolute
temperature is doubled,
the volume is doubled.

V  T (n,P constant)
6
 Avogadro’s Law: Volume and
Amount
The Volume–Amount
Law:
• At constant pressure and
temperature, the
volume of a gas is directly
proportional to the
number of moles of the
gas present.

(P,T constant)
7
Gay-Lussac’s Law: Pressure and
Temperature
For a fixed amount of gas at a constant
volume, the pressure of a gas is directly
proportional to its Kelvin temperature.
P  T

8
 Combined Gas Law
Since PV, V/T and P/T all have constant values for fixed
amount of gas, these relationships can be merged into
a combined gas law, which holds true whenever the
amount of gas is fixed.

9
 The Ideal Gas Law
Ideal gases obey an equation incorporating the laws of
Charles, Boyle, and Avogadro.

1 mole of an ideal gas occupies 22.414 L at STP

STP conditions are 273.15 K and 1 atm pressure
R is a proportionality constant called the ideal gas
constant, which has the same value for all gases:

R = 0.08206 L·atm·K–1mol–1 (if P = atm, V = L)

R = 8.314 JK-1mol-1 (if P = Pa, V = m3)
R = 62.36 L torr K-1 mol-1 (if P = torr, V = L)

10
 The Ideal Gas Law
• Density and Molar Mass Calculations:

• You can calculate the density or molar mass (M) of

a gas. The density of a gas is usually very low
under atmospheric conditions.

11
 Stoichiometric Relationships
with Gases
• We can now combine gas law problems with
stoichiometry problems.

• For instance, if we know the temperature, volume, and

pressure of a gas reactant or product, we can
calculate
the amount (mol) from the ideal gas law, and use the
coefficients of the balanced equation to convert that
into
moles of another reactant or product
amount A amount B
P,V,T of gas A P,V,T of gas B
(in moles) (in moles)

12
 Dalton’s Law of Partial
• The total pressurePressures
exerted by a mixture of gases in a
container at constant V and T is equal to the sum of the
partial pressures exerted by each individual gas in the
container

Ptotal = P1 + P2 + P3 + …..

Dalton’s law allows us to work with mixtures of gases.

13
 Dalton’s Law of Partial
Pressures
• For a two-component system, the moles of
components A and B can be represented by the
mole fractions (XA and XB).

14
 Dalton’s Law of Partial
Pressures
• Mole fraction is related to the total pressure by:

15
 Kinetic Molecular Theory of
Gases
• This theory presents physical properties of gases in terms
of the motion of individual molecules.
• The kinetic-molecular theory is based on the following
assumptions:
1. A gas consists of tiny particles, either atoms or
molecules, constantly moving about in straight lines until
they collide with another particle or the wall of the
container.

2. The size of the gas particles is negligibly small

compared to the total volume of the gas. Most of the
volume of a gas is empty space.
16
 Kinetic Molecular Theory of
Gases
3.The average kinetic energy of the gas particles is
directly
proportional to the temperature of the gas in Kelvin.
There is a distribution of velocities in a sample of
gas — some particles are moving faster and some
are moving slower — but the higher the temperature, the
greater the average kinetic energy is. (EK = ½mv2)

17
 Kinetic Molecular Theory of
Gases
4.The collisions of particles with each other or with the
walls of the container are completely elastic.
When the particles collide, they may exchange energy,
but there is no overall loss of energy: the total kinetic
energy of the gas particles is constant at constant T.
The gas particles do not attract each other, so there is
no “stickiness” to the particles.

18
 Gas law summary

(a) Decreasing the volume of the gas at constant n and T increases the frequency of
collisions with the container walls and therefore increases the pressure (Boyle’s law).
(b) Increasing the temperature (kinetic energy) at constant n and P increases the volume
of the gas (Charles’ law).
(c) Increasing the amount of gas at constant T and P increases the volume (Avogadro’s
law).
(d) Changing the identity of some gas molecules at constant T and V has no effect on
the pressure (Dalton’s law). 19
 Behavior of Real Gases
• Real gases are gases that deviate from “ideal gas law”
but under most conditions, these deviations are slight.
• The actual molar volumes of real gases are not exactly
22.4 L, but they are fairly close (more later).

20
Behavior of Real Gases
The behavior of real gases is often quite a bit different
from that of ideal gases, especially at very low
temperatures or very high pressures.

Ideal gases assumptions

Molecules in gaseous state do not exert any force,

either attractive or repulsive, on one another.

Volume of the molecules is negligibly small

compared with that of the container.

21
 Behavior of Real Gases
• However, at higher pressures, particles are much
closer together and attractive forces become more
important.

Molecules attract one another at distances up to about 10

molecular diameters. The result of the attraction is a decrease
in the actual volume of most real gases when compared with ideal
gases at pressures up to 300 atm.
22
 Behavior of Real Gases
• The volume taken up by gas particles is actually less
important at lower pressures than at higher pressure.
As a result, the volume at high pressure will be greater
than the ideal value.

The volume taken up by the gas particles themselves is less important

at lower pressure (a) than at higher pressure (b).
As a result, the volume of a real gas at high pressure is somewhat larger
than the ideal value
23
 Behavior of Real Gases
Corrections for non-ideality require van der
Waals equation.

Correction for Correction for

intermolecular gas particle
attractions volume
24