Anda di halaman 1dari 79

Chapter 2 Gases

Barometer
This device was invented by Torricelli in 1643 to measure the atmospheric pressure.
1 atm = 760 mm Hg

A Torricellian Barometer

Manometer

Device for measuring the pressure of a gas in a container

Units of pressure
1 standard atmosphere = 1 atm = 760 mm Hg = 760 torr

Pressure =

Force Area

(N) (m2)

1 N/m2 = 1 Pa

1 atm= 101325 Pa = 105 Pa

The gas laws


When studying gases, there are four common variables: Volume, V Pressure, P Temperature, T Amount, # of moles, n Three common laws were developed to see the effects of Pressure, Temperature and Moles on the Volume of a gas (Boyle, Charles and Avogadro). A fourth law describes the effect of temperature on the pressure of a gas (Guy-Lussac).

Boyles law (P,V)

For a given amount of gas and at a constant temperature, the product of the pressure and volume is constant.
J tube

PV = k

Boyles law (P,V)

PV=k P vs. V Hyperbola V=k P y = mx + b

V vs. 1/P Straight line

Boyles law (P,V)


Boyles law describes approximately the relationship between pressure and volume.

A gas that obeys Boyles law is called ideal gas

A plot of PV vs. P for several gases

Boyles law (P,V)


In a study to see how closely gaseous ammonia obeys Boyles law, several volume measurements were made at various pressures using 1 mol of NH3 at 0C.
Experiment 1 2 3 4 5 6 Exp. k=PV 1 22.37 2 22.32 Pressure (atm) 0.13 0.25 0.3 0.5 0.75 1 3 22.31 4 22.25 Volume (L) 172.1 89.28 74.35 44.49 29.55 22.08 5 22.16 6 22.08

Boyles law (P,V)

The dashed line shows the extrapolation of the data to zero pressure to give the ideal value of PV of 22.41 L.atm.

A plot of PV vs. P for ammonia

Charles law (V, T)


For a given amount of gas and at constant pressure, the volume increases linearly with the temperature.

Tk = Tc + 273

Charles law (V,T)


For a given amount of gas and at constant pressure, the volume increases linearly with the temperature.

V=bT

Charles law (V,T)

Effect of Decreased Temperature on a Balloon Filled with Air

Charles law (V,T)

Avogadros law (V,n)


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

V=an

V is the volume of the gas n is the number of moles a is a proportionality constant

Avogadros law (V,n)

Gay-Lussacs Law (T,P)


For a gas at constant volume and mole number, the pressure is directly proportional to the temperature.

P=cT

P is the pressure of the gas T is the temperature of the gas c is a proportionality constant

The ideal gas law


Boyles law: Charles law: Avogadros law: V = k/P V = bT V = an (at constant T and n) (at constant P and n) (at constant T and P)

T is always in K

R is the combined proportionality constant called the universal gas constant = 0.08206 L atm K-1 mol-1

The ideal gas law

This equation defines the behavior of an ideal gas. It expresses behavior that real gases approach at low pressures and high temperatures. Most gases obey this equation closely at pressures below 1 atm.

Boyles Law for a fixed amount at constant temperature PV = constant PV = nRT P1V1 = P2V2 Charless Law for a fixed amount at constant pressure V increases linearly with T V = (nR/P)T Avogadros Law for a fixed temperature and pressure V increases linearly with n V = (RT/P)n

Example 1
A gas sample in the laboratory has a volume of 45.9 L at 25.0C and a pressure of 743 mm Hg. If the temperature is increased to 155C by compressing the gas to a new volume of 31.0 L what is the pressure in atm?

Example 2
Calculate the pressure (in atm) in a container filled with 5.038 kg of xenon at a temperature of 18.8C, whose volume is 87.5 L.

Example 3
Sodium azide (NaN3) is used in air bags in automobiles. Write a balanced chemical equation for the decomposition of NaN3 into N2(g) and Na(s). Calculate the volume in liters of nitrogen gas generated at 21.0C and 823 mm Hg by the decomposition of 60.0 g of NaN3.

Molar volume
Suppose that we have 1 mole of an ideal gas at 0C (273K) and 1 atm. From the ideal gas law, the volume of the gas is 22.42 L. nRT = 22.42 L V= P Molar volume of an ideal gas is 22.42 L

Molar volume
Molar volume of an ideal gas is 22.42 L

The condition of 0C (273K) and 1 atm is called standard temperature and pressure

Molar mass
n= m Molar mass
m (RT)

P=

nRT V

(m/molar mass)RT V

V (molar mass) molar mass

d RT

d RT Molar mass = P

Daltons law
For a mixture of gases in a container, the total pressure exerted is the sum of the pressures that each gas would exert if it were alone. Ptotal = P1 + P2 + P3 +

P1 =

n1RT V

P2 =

n2RT V

P3 =

n3RT V

Ptotal = ntotal

RT V

Daltons law
The fact that the pressure exerted by an ideal gas is not affected by the identity (structure) of the gas particles reveals two things: The volume of the individual particles must not be important. The forces among these particles must not be important.

Daltons law
The mole fraction is the ratio of the number of moles of a given component in a mixture to the total number of moles in the mixture.

1 =

n1 = ntotal

P1 Ptotal

Daltons Law: Gases can be collected by displacement of water

Example 4
A sample of solid potassium chlorate (KClO3) was heated in a test tube and decomposed according to the following reaction: 2KClO3 (s) 2KCl (s) + 3O2 (g) The oxygen produced was collected by displacement of water at 22C at a total pressure of 754 torr. The volume of the gas collected was 0.650 L, and the vapor pressure of water at 22C is 21 torr. Calculate the partial pressure of O2 in the gas collected and the mass of KClO3 in the sample that was decomposed.

Whats behind the ideal gas law?


A purely empirical law - solely the consequence of experimental observations. Explains the behavior of gases over a limited range of conditions. A macroscopic explanation. Says nothing about the microscopic behavior of the atoms or molecules that make up the gas.

Kinetic Molecular Theory of gases


1. Volume of individual particles can be assumed to be negligible (zero). 2. Collisions of particles with container walls are the cause of the pressure exerted by gas. 3. Particles exert no forces on each other. 4. Average kinetic energy is directly proportional to the Kelvin temperature of the gas.

Kinetic Molecular Theory of gases

Random Movement of an Ideal Gas Particle in a box

Calculating the Components of Velocity

Calculating the Components of Velocity uxy2= ux2 + uy2 u2= uxy2 + uz2 u2= ux2 + uy2 + uz2
where u is the speed of the particle and ux, uy and uz are the components of the velocity along the three principal cartesian axes. Note that u is a scalar quantity and conveys no directional information.

Calculation of the Force Exerted on a Container by Collision of a Single Particle

Consider the force exerted on the wall by the component of velocity along the x axis.

Calculation of the Force Exerted on a Container by Collision of a Single Particle

Calculation of the Pressure in Terms of Microscopic Properties of the Gas Particles

Comparison

PV = 2 (KE) T avg n 3

(From theory)

PV = RT n

(From experiment)

The theory agrees with the experiment The KMT is a valid model

The Kinetic Theory Relates the Average Kinetic Energy of the Particles to Temperature

PV = 2 (KE) = RT avg n 3

(KE)avg = 3/2 R T The Kelvin temperature is an index of the average KE of gases (random motion)

Root Mean Square Velocity


The square root of is called the root mean square velocity urms:

R = 8.3145 J/mol K T: in Kelvin M: molar mass in kg/mol

Molecular Speed Distribution


Not all molecules have the same speed. But what is the distribution of speeds in a large number of molecules? The kinetic theory predicts the distribution function for the molecular speeds.

Relative Number of O2 Molecules at STP

Relative Number of N2 Molecules at Three Temperatures

The Mathematical Description of the Maxwell-Boltzmann Speed Distribution

Most probable velocity: ump = square root of 2RT/M

Average velocity: uavg = square root 8RT/M

R = 8.3145 J/mol K T: in Kelvin M: molar mass in kg/mol

An ideal gas particle velocities (m/s)


Root mean square velocity: urms = square root of 3RT/M Most probable velocity: ump = square root of 2RT/M Average velocity: uavg = square root 8RT/M
R = 8.3145 J/mol K T: in Kelvin M: molar mass in kg

Velocity distribution for nitogen gas at 273 K

Effusion: Passage of Gas Through a Pinhole into an Evacuated Chamber

Rate of effusion = 1 / M Grahams law of effusion: Rate of effusion of gas1 = M2 Rate of effusion of gas 2 M1

Diffusion: describes the mixing of gases


When HCl(g) and NH3(g) meet in the tube, a white ring of ammonium chloride NH4Cl(s) forms.

vHCl = 450m/s and vNH3 = 660m/s at 25C.

Relative Diffusion Rates of NH3 and HCl

Diffusion: describes the mixing of gases


vHCl = 450m/s and vNH3 = 660m/s at 25C.

Relative Diffusion Rates of NH3 and HCl

dNH3 uAvg(NH3) MHCl = = 1.5 = dHCl uavg(HCl) MNH3 dNH3 dHCl = 1.3
Experimentally

Theoretically

Smaller mass higher velocity higher intermolecular collisions slower flow NH3 travels a smaller distance to meet HCl than is expected from Grahams law.

Collisions of gas particles with the container walls


ZA uavg (average velocity) ZA A (area) ZA N/V (number of particles per unit volume = number density of particles.

m2

(molecules)/m3

Intermolecular collisions

V = (d2) (uavg) (1s)

Mean free path


Distance between collisions

Time between collision (s)

Distance traveled per second

Real gases

Plots of PV/nRT vs. P at 200 K

Real gases

Plots of PV/nRT vs. P for Nitrogen Gas

Low temperatures & High pressures

Real gases
V nb

nb: is for n moles. b: Correction factor that takes into account the proper volume of 1 mole of gas particle nRT P = V - nb

Real gases
Pobs = P - correction factor nRT = V nb nRT = V nb -a V - correction factor n
2

a: Correction factor that takes into account the mutual attraction of gas particles.

Real gases
Van Der Waals Equation:The Real Gases Equation
Correct ideal gas behavior when at high pressure (smaller volume) and low temperature (attractive forces become important).

Real gases

Low value of a

weak intermolecular forces

b increases with the size of the gas molecule

Exercise 38 (5th edition) Exercise 40 (6th edition)

Exercise 39 (5th edition) Exercise 41 (6th edition)

Exercise 42 (5th edition)

Exercise 43 (5th edition) Exercise 45 (6th edition)

Exercise 45 (5th edition) Exercise 49 (6th edition)

Exercise 49 (5th edition) Exercise 53 (6th edition)

Exercise 58 (5th edition) Exercise 64 (6th edition)

Exercise 63 (5th edition) Exercise 73 (6th edition)

Exercise 64 (5th edition) Exercise 74 (6th edition)

Exercise 66 (5th edition) Exercise 76 (6th edition)

Exercise 67 (5th edition) Exercise 77 (6th edition)

Exercise 72 (5th edition) Exercise 82 (6th edition)

Exercise 73 (5th edition) Exercise 83 (6th edition)

Exercise 80 (5th edition) Exercise 88 (6th edition)

Exercise 81 (5th edition) Exercise 89 (6th edition)

Exercise 100 (5th edition) Exercise 108 (6th edition)

Exercise 106 (5th edition) Exercise 114 (6th edition)

Anda mungkin juga menyukai