Gas Laws:

These laws show the relations between pressure (p), volume (v), temperature (t) and moles (n). 1. Boyles Law: Relates pressure to volume (temperature is kept constant). For a certain amount of gas (number of moles constant) and at a constant temperature, the volume occupied by the gas is inversely proportional to the pressure applied in the gas.
1 p k v = p

Moles and temperature are constant Moles and temperature are constant Moles and temperature are constant Moles and temperature are constant

p.v = k p1.v1 = p2.v2

Graphical representation of Boyles law: Volum e / 3 dm

Pressure / atmosphere
1 1

v = k p (v is y and p is x). as a result y = kx, therefore its a linier function (straight line):

Volum e / dm3

This is because in this point the gas already liquidizes and so gas laws breaks

(1/p) / Atmosphere Pressu re x Volum e

p.v = k

Pressure / Atmosphere 2. Charles Law: Relates volume and temperature (moles and pressure being constant). For a certain amount of gas at constant pressure, the volume occupied by the gas is directly proportional to its temperature in Kelvin.

V T V = KT K=
V T

Moles and pressure are constant Kelvin = oC

V1 V2 V1 T = = 1 OR T1 T2 V2 T2

Graphical representation of Charles law: Volum e / dm3

This is because in this point the gas already liquidizes and so gas laws breaks

Volum e / 3 dm

Temperature / Kelvin

Pressure /atmosph ere -273 o C Temperature / oC

3. Gay-Lussacs Law [Pressure Law]: Relates temperature and pressure (moles and volume being constant). For a certain amount of gas, at constant volume the pressure of the gas is directly proportional to its temperature in Kelvin.

Temperature / Kelvin

4. Combined Gas Laws: Relates pressure, volume and temperature (moles being constant).
1 P

Boyles Law
V T Charles Law T K T V V = PV = KT P P P V1 P V P V 1 = 2 2 K = T1 T2 T

Therefore, if: Ideal Gas Equations:

V 1 P V T V n

V1 V = 2 T1 T2 P P 1 = 2 Volume is Constant: T1 T2 Temperature is Constant: P V1 = P 2V2 1

Pressure is Constant:

Boyles Law (moles and Temperature constant) Charles Law (moles and pressure constant) Common Sense (Pressure and Temperature

constant)

n T V P

V =

n T K P

V P =nRT

T V P =nK K is replaced by a letter R which is a gas

What is the numerical value of the gas constant, R?

Note: At standard temperature and pressure (STP) one mole of any gas occupies 22.4 dm3 ST = 0oC = 273 Kelvin SP = 1 atmosphere = 101.3 KPa (Kilo Pascal) Take one mole of a gas at Standard temperature pressure V P =nR T P = 1 atm, v= 22.4 dm3, n=1 mole, T = 273 K, R=?
1atm 22 .4dm 3 = mole R 273 K 1 3 22 .4atm .dm R= R = 0.0821 atm.dm3.mol-1.K-1 273 mol .K

When P is 101.3 KPa (Kilo Pascal) Pa = N/m2 (neuton/meter2) P = 101.3 x 103 N/m3 V P =nRT
101 .3 10 3 N / m 2 22 .4 10 3 m 3 = mole R 273 K 1 3 3 101 .3 10 .4 10 Nm 22 R= R = 8.314 Nm.mol-1K-1 273 mol .K

R = 8.314 J.mol-1K-1 Note: if you are given the volume of gas in dm3 and a pressure in KPa there is no need to convert KPa into Pa or dm3 into m3 because the conversion factors cancel each other.
m M

Deriving an equation relating density of a gas to temperature and pressure:

V P =nRT

.. n=

m V P = R T M [ V P M =mRT ]/V m P M = RT V P M =dRT . d = density

Kinetic Energy (K.E) of gasses: 1. Any gas is composed of tiny particles which are in continuous random motion bombarding the walls of the container, hence, causing pressure. 2. There collisions with the walls are absolutely elastic (not accompanied by any energy loss). 3. The kinetic energy of the molecules/particles is directly proportional to the temperature of the gas, i.e. K.E T. 4. There are no attracted forces what so ever between the molecules of a gas and so the molecules behave independently. 5. The actual volume of a gas is negligible compared to the volume of the container its in. Deviation from ideality (real gasses):

A gas can behave ideally when at low pressure and high temperature where the volume will be too large and the intermolecular distance will be too large making postulates 4 and 5 applicable whereby there will be no attractive forces and the actual volume of the molecules will be really negligible compared to the volume of the container and the equation V P =nRT can be applied safely however, at the other extreme of high pressure and low temperature the volume allowed for the gas will then be pretty small and so: The volume of the molecules themselves becomes comparable to the volume of the container. There will be some attractive forces between the molecules due to the short distances between the molecules. This means that postulates 4 and 5 break them and the ideal gas equation needs to be modified to account for this: V P =nR T .. When ideal (V b) ( P +a )=nR T .. When real a to compensate or the pressure loss as a result of attractive forces then. b to account for the volume of the molecules compared to the volume of the container. The above equation is a rough equation of what is called Van Der Waals equation describing the behavior of a real gas.
P V Z = nT R

Another approach of handling deviation from ideality the

compressibility factor Z( Z = P V nT R

):

Z< 1 -- Pressure is Z=1 Z> 1 -- Pressure is under estimated gases: over estimated Grahams Law of diffusion of

Pressure / Atmosphere

Under the same conditions of temperature and pressure, the rate of diffusion of a gas is inversely proportional to the square root of its molar mass.

Therefore, V
V =

1 M

V: Velocity, M: Molar mass

K , therefore for two gasses A and B M K V A = ------ Equation 1 MA VB = K MB

------ Equation 2

Divide equation 1 by 2 VA K K Therefore, V = MA MB B

MB VA K = VB K MA MB VA = VB MA

VA MB = VB MA

Exercise: Calculate the ratio between the rates of diffusion of H2 and O2 MO VH = VO MH

2 2 2 2

VH 2 VO2 VH 2 VO2

= =

32 2 16 =4 1
1 ---- T: Time T

Therefore, H2:O2 4: 1

Since V
V = K T

MB VA = VB MA MB TB = TA MA

T A = M B K MA TB

Therefore, the time needed for a certain amount of gas to diffuse is directly proportional to the square root of it molar mass.

Exercise: It requires a certain volume of HBr to diffuse 162 seconds, what time is needed for the same volume of SO2(g) to diffuse under the same conditions. M [HBr] = 80 + 1 = 81 g.mol-1 M [SO2] = 32 + (16x3) = 64 g.mol-1
M HBr THBr = TSO 2 M SO 2
12 6 8 1 = TSO 2 6 4

12 6 9 = x 8 8 162 x = = 144 seconds 9

Exercise: Consider the diagram below: B Cotton soaked in NH3 NH3 (g) + HCl (g) NH4Cl(s)

White smoke of NH4Cl

A Cotton soaked In HCl

80 cm

At what distance from the terminal A will the fumes form?

M HCl d NH 3 = d HCl 2 M NH 3
x 3 .5 6 = 8 x 0 1 7

x = .4653 (80 x ) 1 x =117 .223 1.4653 x +1.46653 =117 .223 117 .223 x= 2.4653 x = 47 .54 80 (47 .54 ) = 32 .5 cm

x = .4653 1 80 x

How can grahams law be obtained from the kinetic theory of gasses? Postulate 3: The kinetic energy of a gas is directly proportional to its temperature in Kelvin

For two different gasses A and B at the same temperature, they will have the same kinetic energy. Therefore, K .E A = K .E B ---- at the same temperature (K.E Kinetic Energy)
1 1 2 2 m A v A = mB v B 2 2
2 2 m A v A = mB v B

2 v A mB = 2 vB m A

vA = vB vA = vB

mB mA mB L mA L mB mA

vA = vB

Daltons law of total pressure of a mixture of non-reacting gasses: In a mixture of non-reacting gasses A, B and C Ptotal = PA + PB + PC Example: TAP VESSEL Gas A V = 1 dm3 PA=0.6 atm Gas B

V = 2 dm3 PB=1.8 atm If the tap between the two vessels is opened, what would the total pressure be then?
P = 0.6 atm 1

GAS A:

V1 = 1dm 3 P2 = unknown V2 = 3dm 3

Boyles Law P1V1 = P2V2 0.6 x 1 = P2 x 3 P2 = 0.2 atm

P = 1.8atm 1

GAS B:

V1 = 2 dm 3 P2 = unknown V2 = 3dm 3

Boyles Law P1V1 = P2V2 1.8 x 2 = P2 x 3 P2 = 1.2 atm Therefore, Ptotal = PA + PB = 1.2 + 0.2 = 1.4 atm Another edition of Daltons law of partial pressure: In a mixture of non-reacting gasses the partial pressure of a gas is directly proportional to its mole fraction. Mole Fraction (X): is equal to moles of that gas divided by total moles of gasses as shown: n XA = A ntotal PA = XA x Ptotal Example: a container contains 64 grams of CH4, 64 grams of SO2 and 64 grams of O2. The total pressure pf this gas mixture is 10.5 atm. Find the partial pressure of O2.
64 = 4 moles 16 64 n(SO2) = = 1 mole 64

n(CH4) =

n(O2) = = 2 moles
PO2 X O2 Ptotal = n( O ) PO2 = 2 Ptotal ntotal
2 P 2 10 .5 = 3 atm O = 7

Law of reacting volumes of gasses: Under the same conditions of temperature and pressure, gasses react together in a volume ratio which is itself the mole ratio

Example: consider the reaction N2(g) + 3H2(g) 2NH3(g). If 5 dm3 of N2 are mixed with 18dm3 of H2 at the same conditions of temperature and pressure and allowed to react: 1. Which of the two gasses is the limiting reactant? N2(g) + 3H2(g) 2NH3(g)
5dm3 18 dm3

V(H2) is needed to react with all N2(g) = 5 = 15dm3 needed V(H2) needed < V(H2) available 15 dm3 < 18 dm3 Therefore, H2 is in excess and N2 is the limiting reactant 2. Describe the composition of the reaction mixture after the reaction is complete V(NH3) forming = 5 = 10 dm3 V(H2) remaining in excess = 18-15 = 3 dm3 Therefore, reaction mixture contains: - Nothing of N2 - 3 dm3 of H2 - 10 dm3 of NH3 Question 1 (a) A certain amount of gas occupies a volume of 420 cm3 at 1.2 atm and a temperature of 27oC. What is the volume will this amount of gas occupy at: P1 = 1.2 atm V1 = 420 cm3 T1 = 300 K (i) 6 atm (temperature kept constant) P2 = 6 atm T2 = 300 K V2 = ?? Boyles Law P1V1 = P2V2 1.2x420 6xV2 V2 =
1.2 420 = 84 cm3 6

3 1

2 1

(ii) 127oC (pressure kept constant) P2 = 1.2 atm T2 = 127+273 = 400 K V2 = ?? V1 V2 420 V2 = Charles Law = T1 T2 300 400
V2 = 400 420 = 560 cm 3 300

(iii 6 atm and 127oC ) P2 = 6 atm T2 = 400 K V2 = ??

PV1 PV 1 1 = 2 2 .2 420 = 61 V2 Combined gas law T1 T2 300 273
V2 =

(iv STP ) P2 = 1 atm T2 = 273 K V2 = ??

400 1.2 420 = 112 cm 3 300 6

PV1 PV 1 1 = 2 2 .2 420 = 1V2 Combined gas law T1 T2 300 273

V2 = 273 1.2 420 = 459 cm 3 s. f . to 3 300 6

(b)

Given that the sample of gas in Part (a) weighs 0.9009 grams, which gas of the following could be under consideration: - C4H10 - C3H8 - C2H6 - CH4 P1 = 1.2 atm V1 = 420 cm3 T1 = 300 K M = 0.9009 grams PV = nRT 1.2 x 0.42 = n x 0.0821 x 300
1.2 0.42 = 0.0205 moles 0.0821 300 m 0.9009 n= 0.0205 = M M

n=

M = 44 g.mol-1 Therefore, the gas is C3H8 Question 2 The density of the liquid water 1 g.cm-3 (i) What volume will 1 gram of liquid water occupy. Mass (g) = volume (cm3) x density (g.cm-3) 1=vx1 V = 1 cm3

(ii) What volume will 1 gram of water vapor occupy at the boiling

point of water at 1 atm 1 gram of H2O (Vapor): gas P = 1 atm T = 373 K V = ?? n=

m 1 = M 18

PV = nRT 1xV=
1 x 0.0821 x 373 18

V = 1.7013 dm3 = 1701.3 cm3 (iii How do your answers to (i) and (ii) verify one of the postulates ) in the kinetic theory of gasses? Notice that the volume occupied by one gram mass water vapor is 1701 while the volume occupied by 1 gram mass liquid water is just 1 cm3, this means that the actual volume of the gas molecules (1) is really negligible compared to the volume in which the gas spread, this verifies postulates 5 in the kinetic theory of gasses. Question 3 Consider the following data which describes how the volume of a certain amount of gas changes with pressure at constant temperature P/atm V/dm3
1 /atm P

1 6
1 6

1.5 2 4
3 8

2.5 3 2.4 2
25 24 3 2

4
8 3

5
25 6

10 0.6
50 3

3
2 3

1.5 1.2 1
6

PV/atm.d m-3

(i) Complete the table above (ii) Plot three graphs relating: a) Pressure(X-axis), Volume(Y-axis): Volum e / 3 dm

Pressure / Atmosphere

b) Volum e / 3 dm

1 (X-axis), Volume(Y-axis): P

c) Pressure(X-axis), PV(Y-axis): Pressu re x Volum e

(1/p) / Atmosphere

Pressure / Atmosphere (iii Which gas law is verified by the graphs? ) Boyles Law (iv At what conditions in the data above is the gas least ideal? ) Least ideal gas is the last data where pressure is 10 atm and volume is 0.6 atmosphere Question 4: Consider the data below that shows how the volume of a certain amount of gas varies with temperature at constant pressure T/oC T/K -23 27 25 0 30 0 77 35 0 12 7 40 0 17 7 45 0 227 500

V/cm3

50 0

60 0

70 0

80 0

90 0

100 0

a) Complete the table above b) On the two separate graphs plot two graphs relating temperature, T, once in oC and another in Kelvin (X-axis) to volume, v/cm3 (Y-axis). 1 In Kelvin: Pressure /atmosph ere

Temperature / Kelvin 2 In oC: Volum e / 3 dm

Temperature / -273 c) Extrapolate each graph downwards until the graph cuts the o o C C (X-axis) Shown above d) What is the significance of the X-intercept of each graph? In graph 1 the X-intercept is 0 In graph 2 the X-intercept is -273 e) Why should part of the extrapolation be shown as a dotted line? This is because in this point the gas already liquidizes and so gas laws breaks f) At what conditions in the table wa the gas least ideal? Why? At the least temperature which is at -23 oC (250 Kelvin) g) Which gas law is verified by the data and the graphs? Charles Law Question 5: a) Derive the equation relating the density of a gas to pressure and temperate PM=dRT

PV = nRT
PV = m RT M

PVM = mRT
PM = m m RT (d= ) V V

PM = dRT b) Show that

d1 P T2 = 1 d 2 P2T1

PM = dRT Apply the equation above for (P1, T1) and (P2, T2) P1M = d1RT1 equation 1 P2M = d2RT2 equation 2 Derive equation 1 by 2 PM d RT 1 = 1 1 P2 M d 2 RT 2 P dT 1 = 1 1 P2 d 2T2 PT d 1 2 = 1 . Q.E.D P2T1 d 2 d) What is the significance of the equation
d1 P T2 = 1 d 2 P2T1 The significance of the equation above is that it shows that the density of the gas is directly proportional to pressure and inversely proportional to temperature, this is because pressurizing a gas more will decrease the volume occupied

since d =

m a smaller volume implies a higher density as for V

the inverse relation between temperature and density it is explained as follows: higher temperature implies larger volume and so lower density. Question 6: a) Cyanogen is an extremely poisonous gas of formula C2N2. what volume will 2.9 grams of this gas occupy at STP Method 1: n(C2N2) =
m 3.9 = =0.075 mole M 5 2

PV = nRT . STP: P = 1 atm, T = 273K 1xV = 0.075x0.0821x273 V = 1.68 dm3 Method 2: At STP 1 mole of a gas occupies 22.4 dm3 V(occupied) = 0.075x22.4 = 1.68 dm3 b) In the reaction below: TNT(explosive) + Oxygen Carbon dioxide + Water vapor

+ Nitrogen C7H5N3O6(s) + O2(g)

CO2(g) + H2O(g) + N2(g) 28CO2(g) + 10H2O(g) +

i) Balance The equation above 4C7H5N3O6(s) + 21O2(g) 6N2(g)

ii) What total number of moles of gasses will result from exploding 45.4 Kg sample of this explosive? M[TNT] = (7x12) + 5 + (3x14) + (16x6) = 227 g.mol-1
m 45400 = = 200 moles M 227 44 n[gasses] = x 200 = 2200 moles 4

n[TNT] =

iii) If this sample is confined in a spherical hole of radius one meter, and the temperature rises to 727oC after the explosion, calculate the pressure exerted by the gasses on the hole hence explain the huge destructive effect of this explosive. Vsphere =
4 4 3 = r 1) 3 = 4.19 m3 x 1000 = 4190 dm3 ( 3 3

PV = nRT P(4190) = 2200 x 0.0821 x 1000 P = 43.1 atm Therefore, this high pressure cause by the gasses will cause a big damage if occurs in a small building or a car or so, as a result, the container will burst. c) Gasses react in a volume ratio which is the mole ratio (if volume of gasses is measured at the same condition of temperature and pressure). Consider the following reaction: 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) i) What volume of O2(g) is needed to react with 48dm3 of NH3
5 48 = 60dm3 4

ii) If 12 dm3 of NH3(g) are combined with 20 dm3 of O2(g) and the gas mixture is allowed to react to completion, what is the composition of the gas mixture after the reaction is complete? V(O2) needed to react with all NH3 =
5 12 = 15 dm3 4

V(O2) available > V(O2) needed 20 dm3 > 15 dm3 O2 is in excess and NH3 is the limiting reactant
4 12 = 12 dm3 4 6 V(H2O) forming = 12 = 18 dm3 4

V(NO) forming =

Composition of gas mixture is: - 0 dm3 NH3 - 5 dm3 O2 (excess) - 12 dm3 NO - 18 dm3 H2O vapor d) In this reaction: (NH4)2Cr2O7(s) N2(g) + 4H2O(g) + Cr2O7(s) i) What mass of Cr2O3 will remain after the decomposition of 1.26 Kg of (NH4)2Cr2O7 M[(NH4)2Cr2O7] = (2x14) + (8x1) + 2x52) + (7x16) = 252 g.mol-1 n=
m 1260 = M 252

= 5 moles
1 x5 = 5 moles 1

n(Cr2O3) forming =
m M m 5= 152

M[Cr2O3] = (52x2) + (16x3) = 152 g.mol-1 n=

M = 760 grams = 9.76 Kg ii) If the decomposition occurred in a sealed container of volume 5 dm3, at a temperature of 227oC, What will the pressure of the gasses in the container be? n(gasses) =
5 5 = 25 moles 1

PV = nRT P(5) = 25 x 0.0821 x 500 P = 205.25 atm iii) If the Container can resist a pressure of 10 atm, will it burst and explode? The container will burst since the pressure it resists is 10 atm and the pressure releases is around 205 atm