Ideal Gas/1

I
Empirical Properties of Gases 1. Boyles Law and Charless Law

DEAL GAS

Of the three states of aggregation, only gas state allows a simple quantitative description. The present we restrict this description to relations among such properties as mass, pressure, volume and temperature. We shall assume that the system is in equilibrium so that the value of the properties is not change with time as long as the external conditions of system is not altered. A system is in definite state or conditions when all of properties which determined by the state of system have definite value. Thus the state of system is described by specifying values of some or all of its properties. We shall only to talk about 4 properties (m, v, p & t), but the questions, is how many properties must we use to describe completely system? The answer is depend on how accurate the description is required. But usually, only 4 properties are required. The Equation of State of a system is mathematical relationship among the values of these 4 properties. Only 3 of these must be specified to describe the state; and the fourth can be determine from equation of state. The first quantitative measurement of the pressure-volume behavior of gases were made by Robert Boyle (1662). His data give indication that the volume is inversely proportional to the pressure : V = C/p, or, Boyles law can be written in the form: PV = C (1) Its applies only to fixed mass and constant temperature. Figure 1 is plot volume as function of pressure (Boyles Law)

V/dm3

p/atmm

Vo

V/dm3

t/oC

Figure 1: Volume as function of Figure 2: Volume as function of pressure temperature (Charless Law
Later experiment, Charles show that C is function of temperature. This is a raw statement of Charles Law. Through the measurement, Gay-Lussac show the fact that volume of gas with a fixed mass is linear function of temperature, which mathematically can be written: V = a + bt. (2)
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Plot of V as function of temperature is shown at figure 2; b is the slope of curve with t as horizontal axis and V as vertical axis (ordinate). Intercept on the vertical axis is a = Vo, the volume at t = 0oC. The slope of the curve, b, is derivative of V to t at constant p, and can be written: b = t p a = Vo And Gay Lussacs law can be written: V = Vo + t . t (5) p Thermal Expansion Coefficient (0) Thermal expansion coefficient is increased volume relatively to initial volume. So:
V - V0 1 V = V0 t p V0 Combination of 5 and 6, we get:
V V

(3) (4)

0 =

(6) (7)

V = V0 + 0 t For ideal gas; = 1/T, so: 0=

1 1 = T0 273,15

Since T = 273,15 + t, therefore 7 can be written: V= or V = V0 . 0 .T (Gay-Lussacs Law) (9)

V0 . T 273,15

(8)

2. Ideal Gas Law

By Boyles law, we can get V0 = C0/p, and then Gay-Lussacs law (9) can be written as: V=
C 0 . 0 . T p

(10)

with C0 is C at 00C. We have known that Boyles law is can only applied for fixed mass and temperature . If we use C0, the means is we use 00C, then C0 just determined by mass or C0 proportional with mass of gas and can be written as : C0= B.m B is constant while m is mass of gas. So 10 can be written as: V= Or:
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(11)

B . m . 0 . T p

(12)

Ideal Gas/3

m=

pV 1 T B . 0

(13)

If we choose standard condition that is m = M kg/mole (molar mass), P = 1 Pa and T = 273,15 K, V = 0,00224 m3 /mol, then 13 can be written as: M = 8,314 j K-1 mol-1 or: M=R or:
1 M = B . 0 R 1 B . 0 1 B . 0

(14)

Substitution 14 to13, yield: m= or: pV= or: pV=nRT (15)

m RT M

pV M T R

Eq. 15 is usually called as ideal gas equation. If n = 1 mole, ideal gas equation can be written as: p V =RT (16)

3. Daltons Law; Partial Pressure

With V = the molar volume of gas i.e. volume of 1 mole gas.

If in fixed volume (V) , we have the mixture of totally n mole consist as n1 mole gas 1, n2 mole gas 2 and n3 mole gas 3 with n = n1 + n2 + n3 then we have: p = n R T /V p1 = n1 R T/V p2 = n2 R T/V p3 = n3 R T/V (17) (18)

Another relationship is: p = p 1 + p 2 + p3 Combination of 17 with 18 yield: (19)

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n p1 = 1 . p n n2 .p p2 = n n p3 = 3 . p n

And generally written as: pi = or: pi = xi . p (21) with xi adalah mole fraction . And we can look that partial pressure is proportional with its mole fraction
ni .p n

(20)

4. Barometric Distribution
So far, if the ideal gas in the room of container, then we assumed that gas has homogenous pressure at all part of the container. This assumed is true if this container is placed at free gravity region. But , if gravity field works to this container then this assume is completely wrong. Under gravity filed, the molecules more meetings in the bottom than at the top. As a result is, the gas pressure at the bottom is larger than at the top. This is called the barometric distribution. Imagine that we have cylindrical column with bottom area is A and at homogenous temperature T and under influence of gravity field with gravity acceleration = g . The z vertical coordinate is measured from the bottom of column, therefore the value of z at the bottom is = 0. (Figure 3). At any z place, the pressure is determined by mass of fluid from z to up. If this mass is m, the then force given by the fluid is mg, and we get pressure at z position is: p=
m g A

(22)

Now we shall to look the pressure at z+dz. If mass of fluid from this position to up is m and the pressure is p, then we get:
m' g A

p' =

(23)

p dz. p h

z + dz.

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z=0
Figure 3: Column of fluid under gravity field The different of the both equation above is: p'- p = or: dp =

m' g A

m g A

We know that mass (m) = V, then (24) can be written as: dp = or: dp = g
V' V A A
V' g A

m' g A

m g A

(24)

Vg A

(25)

V'/A is the high from z+dz to up or or h - (z+dz) and V/A is the high from z to up or h z, : dp = g { h-(z+dz) - (h - z) } or: dp = -g dz. Remember that: = m/V ; m = n M while V = nRT/p, jadi: (26)

= Mp/RT Substitution 27 to 26, yield: dp = or:

1 Mg d = p dz p RT

(27)

Mg p RT

dz

(28)

Integration of 28 from 0 to z:
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ln pz - ln p0 = - Mgz/RT or:
pz Mg = RT e po
z

or: pz = p0 RT z e with : pz = pressure at z p0 = pressure at the bottom M = Relative molecular mass With ideal gas assumption, we know that pressure of gas is linearly proportional with concentration, and then analog with (29) we may write: Cz = C0 RT z e
Mg Mg

(29)

(30)

Since concentration is linearly proportional with amount of particles (n), we also may write (29) in the following form: nz = n0 RT z e
Mg

(31)

Eq.31, can be developed for calculation amount of particles in the whole of container. Since n0 is constant, so the only variable at right side z. Differential of the both side of (31) is:
dn z = n0 d (
Mg z) e RT

or:
dn z = n0

Mg z dz. e RT

(32)

Integral all space to (32) is:

z M g z R T dz e

nz + c = n0
0

(33)

where c is integration caonstant and nz+c is total amount of particles in the container therefore (33) can be written: n = n0 or:
0 z M g z R T dz e

(34)

n = -n0 .

R T M g

M g z T e R 1

(35)

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or: n = n0 .
R T M g
M g T z 1 e R

(36)

where n is total amount of particles from the botton to z in the container. If we substitute z in (33) with infinity we get: n = n0 .
R T M g

(37)

where n is total amount of particles in atmosphere with the assumption that atmosphere has homogenous temperature T. Note that all above distribution equation not only can be used for gas, bat also can be used for colloidal particle like suspension of polymer compound in liquid medium

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Problems:
1. A sealed flask with capacity of 1 dm3 contains 5 g of ethane. The flask is so weak that it will burst if pressure exceeds 1 MPa. Determine the temperature when the pressure of flask reach bursting pressure. 2. A large cylinder for storing compressed gases has a volume of about 0.050 m3. If the gas is stored under pressure 15 MPa at 300K, how many moles of gases are contained in the cylinder? Determine the mass, if cylinder is contain of the oxygen gas? 3. The coefficient of thermal expansion , is defined by = V T . Using p equation of state, compute the value of for ideal gas.
4. The coefficient of compressibility, is defined by = V p . compute T the value of for ideal gas. 1 V

1 V

5. For an ideal gas, express derivative T

p in terms of and v

6. Helium at 30,20 C is contained at the following system.

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Vacuum b

a L

The leveling bulb L can be raised so as to fill the lower bulb with mercury and force the gas into upper part of the device. Volume the bulb 1 to the mark b is 100.5 cm3 and volum the bulb 2 between the marks a and b is 110.0 cm 3. The pressure exerted by helium is measured by different between the mercury levels in the device and in the evacuated arm of manometer. When the mercury level is at a, the difference in levels is 20.14 mm. The density of mercury at 30.2oC is 13.5212 g/cm3 and the acceleration of gravity is 9.80665 m/s2. Wht is the mass of helium in the container? 7. The same type of apparatus is used as in problem 6. In this case the volume of v1 is not known and the volume of bulb 2, v2 , is 110.0 cm3. When the mercury level is at a the difference in levels is 15.42 mm. When the mercury level is raised to b, the difference in levels is 27.35 mm. The temperature is 30.2 oC. Use the values of density and g given in problem 6. a) What is the mass of helium in the system? b) What is the volume of bulb 1?

8. Consider a gas mixture in a 2 dm3 flask at 27oC. For each mixture, calculate the partial pressure of each gas, the total pressure, and the composition mixture in mole percent, if the mixtures are: a. 1 g H2 and 1 g O2. b. 1 g N2 and 1 g O2. c. 1 g CH4 and 1 g NH3 d. 1 g H2 and 1 g Cl2. 9. A sample of air is collected over water at 20oC. At equilibrium, the total pressure of moist air is 1 atm. The equilibrium vapor pressure of water is 17.54 Torr; the composition of dry air is 78 mole % Nitrogen, 21 mole % oxygen and 1 mole % Ar. a. Calculate the partial pressure of each of gas in wet mixture. b. Calculate the mole fraction of each gas of in wet mixture. 10. Consider 20 L sample of moist air at 60oC under a total pressure 1 atm in which the partial pressure of water vapor is 0.120 atm. Assume that composition of dry air given in problem 9. a) What are the mole percentage of each of gas in the sample?

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b) The percent relative humidity is defined as %R.H.= 100pw/pwo where pw is the partial pressure water vapor in sample and pwo is the equilibrium vapor pressure of water at the temperature in question. At 60oC, pwo = 0.197 atm what volume must the mixture occupy at 60oC if the relative humidity is to be 100%? c) What fraction of water will be condensed if the total pressure of mixture is increased isothermally to 200 atm? 11. A mixture of oxygen and hydrogen is analyzed by passing it over hot copper oxide and through a drying tube. Hydrogen reduces the CuO according to the equation: CuO + H2 Cu + H2O Oxygen then re-oxidizes the copper formed: Cu + 1/2 O2 CuO 100 cm3 of mixture measured at 25oC and 750Torr yield 84.5 cm3 of dry oxygen measured at 25oC and 750Torr after passage over CuO and drying agent. Determine the original composition of the mixture. 12. A gas sample is known to be a mixture of ethane and butane. A bulb of of 200 cm3 capacity is filled with the gas to a pressure 100KPa and at 20oC. If weight of gas in the bulb is 0.3846 g, what is the mole percent ethane and butane in the mixture? 13. Consider an isothermal column of an ideal gas at 25oC . What must the molar mass of this gas, if the pressure at 10 km is 0.8 of its in the ground level ? 14. Assuming that air has a mean molar mass of 28.9 g/mol and that the atmosphere is isothermal at 25oC. Compute the barometric pressure at Denver which 1600m above sea level; compute the barometric pressure at the top of Mt Evans, 4348m above sea level. The pressure at sea level may taken as 760Torr. 15. Consider an ideal potato gas which has following properties: it obeys the ideal gas law, and individual particles have mass of 100 g, but occupy no volume (that is, they are point masses). At 25oC compute the high at which number of potato per cubic metre is 106 of its at the ground level. Note: 1 atm = 1,01325. 105 Pa = 760 Torr g = 9,807 m s-2 R = 8,314 J/K mole

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