gases © 2009, prentice-hall, inc. characteristics of gases unlike liquids and solids, gases...

Gases

© 2009, Prentice-Hall, Inc.

Characteristics of GasesCharacteristics of Gases

• Unlike liquids and solids, gases– expand to fill their containers;– are highly compressible;– have extremely low densities

– Vapor = gaseous state of a substance that is ordinarily liquid or solid

Gases

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• Pressure is the amount of force applied to an area.

PressurePressure

• Atmospheric pressure is the weight of air per unit of area.

P =FA

Gases

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Units of Pressure• Pascals 1 Pa = 1 N/m2

• Bar 1 bar = 105 Pa = 100 kPa

• mm Hg or torr the difference in the heights measured in mm (h) of two connected columns of mercury.

• Atmosphere 1.00 atm = 760 torr

Gases

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Standard Pressure

• Normal atmospheric pressure at sea level is referred to as standard pressure.

• It is equal to– 1.00 atm

– 760 torr (760 mm Hg)– 101.325 kPa

Gases

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Manometer

This device is used to measure the difference in pressure between atmospheric pressure and that of a gas in a vessel.

Gases

Practice with Pressure• On a certain day the barometer in a laboratory

indicates that the atmospheric pressure is 764.7 torr. A sample of gas is placed in a flask attached to an open-end mercury manometer, shown below. The level of mercury in the open-end arm of the manometer has a height of 136.4 mm, and the mercury in the arm that is in contact with the gas has a height of 103.8 mm. What is the pressure of the gas in torr?

in atmospheres?

in kPa?

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Gases

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The Gas LawsThe Gas Laws

BOYLE’S LAW: The volume of a fixed quantity of gas at constant temperature is inversely proportional to the pressure.

Gases

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P and V areinversely proportional

A plot of V versus P results in a curve.

Since

V = k (1/P)This means a plot of V versus 1/P will be a straight line.

PV = k

Gases

Temperature

• Temperature = Average Kinetic Energy

• K = °C + 273

• 0 K = absolute zero

• Standard temperature = 0 °C

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Gases

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Charles’s Law

• The volume of a fixed amount of gas at constant pressure is directly proportional to its absolute temperature.

A plot of V versus T will be a straight line.

• i.e., VT

= k

Gases

Combined Gas Law

• Note: T must be in Kelvin

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Gases

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Avogadro’s Law

• The volume of a gas at constant temperature and pressure is directly proportional to the number of moles of the gas.

• Mathematically, this means V = kn

Gases

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The Ideal Gas EquationThe Ideal Gas Equation

V 1/P (Boyle’s law)V T (Charles’s law)V n (Avogadro’s law)

• So far we’ve seen that

• Combining these, we get

V nTP

Gases

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Ideal-Gas Equation

The constant of proportionality is known as R, the gas constant.

Gases

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Ideal-Gas Equation

The relationship

then becomes

nTP

V

nTP

V = R

or

PV = nRT

Make sure T is in Kelvin!

Gases

• Use ideal gas law to derive relationships between 2 other variables

PV=nRT

if n and T are constant, P1V1 = P2V2

if n and P are constant, V1 = V2

T1 T2

if n and v are constant, P1 = P2

T1 T2

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Relationships between P, V, and T

Gases

Molar Volume• Molar volume = volume that 1 mole of gas

occupies.

• At STP, what is the molar volume of CO2?

• N2?

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Gases

Practice with Gas LawsSuppose we have a gas confined to a cylinder. How

will each of these changes affect the average distance between molecules, the pressure of the gas, and the number of moles of gas present in the cylinder :

(a)Heat the gas from 298 K to 360 K, while maintaining the piston in the same position.

(b) Move the piston to reduce the volume of gas from 1 L to 0.5 L.

(c) Inject additional gas through the gas inlet valve.

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Gases

More practice• Calcium carbonate, CaCO3(s), decomposes upon heating to give CaO(s)

and CO2(g). A sample of CaCO3 is decomposed, and the carbon dioxide is collected in a 250-mL flask. After the decomposition is complete, the gas has a pressure of 1.3 atm at a temperature of 31 °C. How many moles of CO2 gas were generated?

• Tennis balls are usually filled with air or N2 gas to a pressure above atmospheric pressure to increase their “bounce.” If a particular tennis ball has a volume of 144 cm3 and contains 0.33 g of N2 gas, what is the pressure inside the ball at 24 °C?

• The gas pressure in an aerosol can is 1.5 atm at 25 °C. Assuming that the gas inside obeys the ideal-gas equation, what would the pressure be if the can were heated to 450 °C?

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Gases

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Dividing both sides of the ideal-gas equation by V &

RT, we get:

Knowing moles molecular mass = mass, (n = m)

We can multiply both sides by the molecular mass () to get:

nV

PRT=

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PRT

mV

=

n has units of moles/L V

Further Applications of the Ideal Gas Law

Gases

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Densities of Gases• Mass volume = density

• So,

Note: If you know the molecular mass, the pressure, and the temperature to calculate the density of a gas.

PRT

mV

=d =

Gases

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Molecular Mass

We can manipulate the density equation to enable us to find the molecular mass of a gas:

Becomes

PRT

d =

dRTP =

Gases

Practice• What happens to the density of a gas as (a) the gas is heated in a

constant-volume container; (b) the gas is compressed at constant temperature; (c) additional gas is added to a constant-volume container?

• A series of measurements are made to determine the molar mass of an unknown gas. First, a large flask is evacuated and found to weigh 134.567 g. It is then filled with the gas to a pressure of 735 torr at 31 °C and reweighed. Its mass is now 137.456 g. Finally, the flask is filled with water at 31 °C and found to weigh 1067.9 g. (The density of the water at this temperature is 0.997 g/mL.) Assume that the ideal-gas equation applies, and calculate the molar mass of the unknown gas.

• Calculate the average molar mass of dry air if it has a density of 1.17 g/L at 21 °C and 740.0 torr.

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Gases

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Gas Mixtures and Gas Mixtures and Partial PressuresPartial Pressures

• The total pressure of a mixture of gases equals the sum of the pressures that each would exert if it were present alone.

• In other words,

Ptotal = P1 + P2 + P3 + …

Gases

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Partial Pressures

• When one collects a gas over water, there is water vapor mixed in with the gas.

• To find only the pressure of the desired gas, one must subtract the vapor pressure of water from the total pressure.

Gases

Gases in the AirThe % of gases in air Partial pressure (STP)

78.08% N2 593.4 mm Hg

20.95% O2 159.2 mm Hg

0.94% Ar 7.1 mm Hg

0.03% CO2 0.2 mm Hg

PAIR = PN + PO + PAr + PCO = 760 mm Hg 2 2 2

Total Pressure 760 mm Hg

Gases

Partial Pressure & Mole fractionThe mole fraction of an individual gas component in an ideal gas mixture

can be expressed in terms of the component's partial pressure or the moles of the component:

xi = Pi = ni

P n

and the partial pressure of an individual gas component in an ideal gas can be obtained using this expression:

Pi = xi P

xi= mole fraction of any individual gas component in a gas mixture

Pi= partial pressure of any individual gas component in a gas mixture

ni= moles of any individual gas component in a gas mixture

n= total moles of the gas mixture

P= pressure of the gas mixture

The mole fraction of a gas component in a gas mixture is equal to the volumetric fraction of that component in a gas mixture.

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Gases

Practice• What is the total pressure exerted by a mixture of 2.00 g of H2

and 8.00 g of N2 at 273 K in a 10.0-L vessel?

• A gaseous mixture made from 6.00 g O2 and 9.00 g CH4 is placed in a 15.0-L vessel at 0 °C. What is the partial pressure of each gas, and what is the total pressure in the vessel?

• A study of the effects of certain gases on plant growth requires a synthetic atmosphere composed of 1.5 mol percent CO2, 18.0 mol percent O2, and 80.5 mol percent Ar.

(a)Calculate the partial pressure of O2 in the mixture if the total pressure of the atmosphere is to be 745 torr.

(b) If this atmosphere is to be held in a 121-L space at 295 K, how many moles of O2 are needed?

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Gases

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Kinetic-Molecular TheoryKinetic-Molecular Theory

This is a model that aids in our understanding of what happens to gas particles as environmental conditions change.

Gases

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Main Tenets of Kinetic-Molecular Theory

• Gas particles are in constant random straight line motion

Gases

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Main Tenets of Kinetic-Molecular Theory

The combined volume of all the molecules of the gas is negligible relative to the total volume in which the gas is contained.

Gases

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Main Tenets of Kinetic-Molecular Theory

Attractive and repulsive forces between gas molecules are negligible.

An ideal gas is like an ideal vacation! High Temp & Low pressure

Gases

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Main Tenets of Kinetic-Molecular Theory

Energy can be transferred between molecules during collisions, but the average kinetic energy of the molecules does not change with time, as long as the temperature of the gas remains constant.

Gases

Maxwell-Boltzman Distribution

Scheffler

• Molecules are in constant motion

• Not all particles have the same energy

• The average kinetic energy is related to the temperature

• An increase in temperature spreads out the distribution and the mean speed is shifted upward

Gases

Scheffler

The distribution of speedsfor nitrogen gas moleculesat three different temperatures

The distribution of speedsof three different gasesat the same temperature

urms = 3RTM

Velocity of a Gas

Gases

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A sample of O2 gas initially at STP is compressed to a smaller volume at constant temperature. What effect does this change have on (a)the average kinetic energy of O2 molecules, (b) the average speed of O2 molecules, (c) the total number of collisions of O2 molecules with the container walls in a unit time, (d) the number of collisions of O2 molecules with a unit area of container wall per unit time?

PRACTICE

Gases

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Molecular Effusion and DiffusionMolecular Effusion and Diffusion

Effusion is the escape of gas molecules through a tiny hole into an evacuated space.

Gases

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Diffusion

Diffusion is the spread of one substance throughout a space or throughout a second substance.

Gases

GAS DIFFUSION AND GAS DIFFUSION AND EFFUSIONEFFUSION

Graham’s law governs Graham’s law governs effusion and diffusion effusion and diffusion of gas moleculesof gas molecules..

Thomas Graham, 1805-1869. Professor Thomas Graham, 1805-1869. Professor in Glasgow and London.in Glasgow and London.

Rate of effusion is Rate of effusion is inversely proportional to inversely proportional to its molar mass.its molar mass.

Rate of effusion is Rate of effusion is inversely proportional to inversely proportional to its molar mass.its molar mass.

M of AM of B

Rate for B

Rate for A

Gases

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Effusion

The difference in the rates of effusion for helium and nitrogen, for example, explains why a helium balloon would deflate faster.

Gases

Practice• Calculate the rms speed, u, of an N2 molecule at 25 °C.

• What is the rms speed of an He atom at 25 °C?

• An unknown gas composed of homonuclear diatomic molecules effuses at a rate that is only 0.355 times that of O2 at the same temperature. Calculate the molar mass of the unknown, and identify it.

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Gases

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Real Gases: Deviations from Real Gases: Deviations from Ideal BehaviorIdeal Behavior

In the real world, the behavior of gases only conforms to the ideal-gas equation at relatively high temperature and low pressure.

Gases

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Real Gases

Even the same gas will show wildly different behavior under high pressure at different temperatures.

Gases

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Deviations from Ideal Behavior

The assumptions made in the kinetic-molecular model (negligible volume of gas molecules themselves, no

attractive forces between gas molecules, etc.) break down at high pressure and/or low temperature.

Gases

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Corrections for Nonideal Behavior• The corrected ideal-gas equation is known

as the van der Waals equation.

) (V − nb) = nRTn2aV2

(P +

Gases

Practice• If 1.000 mol of an ideal gas were confined to 22.41 L at 0.0 °C, it

would exert a pressure of 1.000 atm. Use the van der Waals equation and the constants in Table 10.3 to estimate the pressure exerted by 1.000 mol of Cl2(g) in 22.41 L at 0.0 °C.

• Consider a sample of 1.000 mol of CO2(g) confined to a volume of 3.000 L at 0.0 °C. Calculate the pressure of the gas using

(a) the ideal-gas equation and

(b) the van der Waals equation.

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