: STATES OF MATTER:

BEDANTA BORA Asst Prof D. R. College Golaghat, Assam bedanta69@gmail.com

Matter exists in three physical states depending upon the magnitude of intermolecular forces and thermal energy possessed by the substance. The most compact form is the solid in which the intermolecular force is maximum and gas in which the intermolecular force is minimum . It is remarkable that the chemical properties of substance do not change with change in its physical state but rate of chemical reaction changes with change in its physical state. The behavior of gasses is governed by the following laws: Boyles law ( Pressure-volume relationship): At constant temperature the volume of a given amount of gas varies inversely with pressure V

T and n(number of moles) constant

V = k Or, PV = k(const.)

This means at definite temperature for a given amount gas, P1V1 = P2V2 = P3V3 = .
T3

pressure(P)

T2 T1 PV

T3 T2 T1

volume(1/V)

pressure(P)

pressure(P)

In the above graph (called isotherm), T1 < T2 < T3 Charles law ( volume temperature relationship):

Charles observed experimentally that if pressure is kept constant the volume of a given amount of gas increases or decreases by part of the original volume of

the gas at 0C. Charles generalized this observation in the form of law stated as: At a constant pressure the volume of a given amount of gas increases or decreases by temperature. If the volume of the gas at 0C be V0 then at 1C, vol V1 would be. V1 = V0 + Volume (Vt) of the gas at tC, Vt = V0 + V0 V0 part of its volume at 0C for each degree rise or fall in

Vt = V0 (

Or,

Vt =

(t + 273.15)

Again, T = tC + 273.15

Or,

Vt = const. x T

const. =

T P and n constant. In other words Charles law may be stated as, At constant pressure the volume of a given amount of gas varies directly to its absolute temperature. Variation of volume of a definite quantity of gas with temperature at constant pressure is shown graphically below. Such graph are called isobar. P1
P1<P2< P3

Or Vt

P2

P3 V -273.15C
Temp(C)
0C

Starting from Charles law, how can you establish the absolute scale of temperature. Ans: If the volume of the gas at 0C and tC be V0 and Vt respectively at given pressure, then by Charles law Vt = V0 + It t = -273.15C , V -273.15C = V0 + V0 V0

Or, V -273.15C = 0 This means at -273.15C, volume of all gasses becomes zero ie. gas cease to exist. P1
P1<P2< P3

P2 P3

-273C

0C

Temp(C)

The temperature -273.15C at which gasses cease to exist ( since volume becomes zero) is called absolute zero. Starting at -273.15C as the lowest temperature called absolute zero, the temperature scale called the absolute or Kelvin scale is fixed. In Kelvin scale tC is (t + 273.15)K ie. T(K) = tC + 273.15 Avagadros hypothesis( volume amount relationship): Under same condition of temperature and pressure equal volume of all gasses contain equal number of molecules.

P & T constant

What is ideal gas equation? Derive it. Ans:Part I: Ideal gas equation is the relationship between the four variables( V, P, T, n ) of gas and describes the state of any gas. It describes the simultaneous variation of the variable. The ideal gas equation is described as PV= nRT. Part II: We have the three gas laws Boyles law, Charles law and Avagadros law: V V V T n
T and n constant P and n constant. P & T constant

On combining these three laws we see that volume of gas depends upon pressure, temperature and number of moles as follows. V

V = R Or PV = nRT The above equation is called the ideal gas equation. R is constant called the universal gas constant and is independent of the nature of gas. Unit for R: We have the ideal gas equation: PV = nRT Or, R=

R=

R=

R=

Or

R=

Hence the SI unit for R is Jmol1K1 Physical significance of R: R is measure of change in energy per mole of gas per degree change in temperature. Numerical value of R: The value of R depends upon the unit in which the variable P, V and T are expressed. In SI unit at N.T.P for one mole of gas, P = 101325 Nm2(Pa) T = 273K V = 22.414 x 103 m3 Now, R = R = Or, R = 8.314 J mol1 K1 Nm mol1 K1

Again if pressure is in atm. and volume in liter, for one mole gas at N.T.P, P = 1 atm T = 273K V = 22.414 liter

Now,

R = L atm mol1 K1

R = Or,

R = 0.0821 L atm mol1 K1

Other values of R: R = 8.314 J mol1 K1 1 cal = 4.184J R = Or, cal mol1 K1

R = 1.987 cal mol1 K1

Density of gas: We have the ideal gas equation, PV = nRT = Or, RT

Here we see that at given temperature and pressure density of gas is directly proportional to molar mass.

Show that, Mol. Weight = 2 Vapour density. Ans: We have, V.D =

By Avagadros hypothesis, equal volume of all gasses under same condition of temperature and pressure contain equal number of molecules. Hence, V.D =

= =

=
or, M = 2 x VD

( Mol wt of H2 = 2)

Show that molar volume of any gas at NTP is 22.4liter. Ans: We have, Mol wt. = 2 x VD or, M = 2x

= 2x
Or , Hence, Mass of 1 litre of gas at NTP = M gm of gas occupy a volume of M gm. or 22.4 litre at NTP

But M gm represent one mole of the gas. Therefore one mole of gas occupies a volume of 22.4 liter at NTP. Daltons law of partial pressure:

According to Daltons law of partial pressure, The total pressure exerted by a mixture of non reacting gas is the sum of the partial pressure of the individual gasses at the same temperature. If p1, p2, p3, be the partial pressure of gasses in the mixture than the total pressure according to Daltons law is, Ptotal = p1 + p2 + p3 + What is partial pressure? Ans: The partial pressure of a gas is the pressure exerted by the gas, when it alone occupies the entire container occupied by the gas mixture at the same temperature. Show that the partial pressure exerted by a gas is proportional to its mole fraction in the mixture. Ans: Suppose we have a gaseous mixture consisting of n1and n2 moles of gasses 1 and 2 occupying volume V at temperature T. Let P1 and P2 be their partial pressure. P1V = n1RT .. (1) P2V = n2RT .. (2) Again, PtotalV= nRT (3) n = n1 + n2
(1)

(3)

=
But, Hence, Or, P1 = x1 = mole fraction of gas-1 P1 = x1 Ptotal x1

ie. partial pressure of gas is proportional to its mole fraction. Grahams law of diffusion: Grahams law of diffusion states, Under the same condition of temperature and pressure the rate of diffusion of gas is inversely proportional to square root of its density. Rate of diffusion( r) If two gasses 1 and 2 has rate of diffusion r 1 and r2 and density d1 and d2, under the same condition of temperature and pressure,

The term rate of diffusion implies the volume of gas diffused per unit time. ie. Rate of diffusion( r) = What is diffusion. How do it differ from effusion? Ans: Diffusion is the process by virtue which non-reacting gasses mix with one another. On the other hand effusion is the process by which gas under pressure escapes through fine hole or orifice. Show that the time of diffusion for gas is directly proportional to square root of iits its molecular weight. Ans: From Grahams law of diffusion,

Here r1, r2 , d1and d2 are the rate of diffusion and density of two different gas 1 and 2 under the same condition of temperature and pressure. Since Mol wt(M) = 2 x vapor density,

Or,

Here, t1 and t2 are the time taken for diffusion for v ml of gasses 1 and 2 under the same condition of temp and pressure. Hence, or, Time of diffusion(t)

Exercise:
(a) Arrange the following gasses in increasing rate of diffusion: CO 2, CH4, H2 and SO2. Ans: CO2( 44 amu), CH4( 16 amu), H2 (2amu) and SO2( 64 amu). Rate of diffusion = SO2 < CO2 < CH4 < H2 [ since, Rate of diffusion ]

(b)Arrange the following gasses in increasing time of diffusion: CO 2, CH4, H2 and SO2. Ans: CO2( 44 amu), CH4( 16 amu), H2 (2amu) and SO2( 64 amu). Time of diffusion = H2 < CH4 < CO2 < SO2 [ since, time of diffusion ]

:KINETIC THEORY OF GASES: Write down the postulates of kinetic theory of gas. Ans: The kinetic theory of gasses was first proposed by Bernoulli and later developed by Boltzmann, Maxwell, Clausius etc to explain he behavior of gasses. The main postulates of the theory are: 1. Gas is composed of minute discrete particles called molecule. Molecules of same gas are alike and different gases are different. 2. Molecules are in random chaotic motion and are colliding with each other and with the walls of the container. 3. The molecules are regarded as point mass ie. volume of the molecules is negligible compared to the volume of the containing vessel. 4. There is no intermolecular force between the molecules. 5. The temperature of the gas is measure of the average kinetic energy of the gas molecule. 6. The pressure exerted by gas is due to bombardment of the gas molecules upon the walls of the container.

7. The molecular collision is perfectly elastic. In between two collision the molecule travel in straight path called free path. Show that the average kinetic energy of gas molecule depends upon the absolute temperature. Ans: From kinetic theory, PV = mNc2

( P= pressure, V= volume, N= number of molecule and m= mass of a gas molecule) Or, PV = = N. N. mc2

k = average KE of a gas molecule

But for one mole gas, PV = RT No.

Hence,

= RT

No = Avogadro number

k
or, Hence,

= = T

. . kT

T k= = Boltzmann constant

k k

We see that the average kinetic energy of gas molecule varies directly to the absolute temperature. Show that the average molar kinetic energy of gasses depends upon the absolute temperature and not upon the molar mass. Ans: From kinetic theory, PV =

mNc2

( P= pressure, V= volume, N= number of molecule and m= mass of a gas molecule)

Or,

PV = =

N. N.

mc2

k = average KE of a gas molecule

But for one mole gas, PV = RT No. Ek =

Hence,

= RT RT

No = Avogadro number

Ek is the average molar kinetic energy of gas. Hence, Ek T

We see that the average molar kinetic energy of gas varies directly to the absolute temperature and not up[on the molar mass. Different types of molecular velocity: According to the kinetic theory of gas, the molecules are in random motion and are moving with different velocity. The different molecular velocity are: 1. Average velocity(u): It is the statistical average of the different velocity possessed by the molecules at a given temperature. If v1, v2, v3vi be the velocity possessed by n1, n2, n3..ni number of molecule, than the average velocity is given by, n1v1 + n2v2 + n3v3 + n4v4 +.......... u = n1 + n2 + n3 + n4............... From kinetic theory of gas, uav =

or,

uav =

( M = N0 m and k =

= Boltzmann constant )

2. Root mean square velocity(urms): It is the square root of the mean square velocity possessed by the molecules at a given temperature. If v 1, v2, v3vi be the velocity possessed by n1, n2, n3..ni number of molecule, than the average velocity is given by, 2 2 2 2 n1v1 + n2v2 + n3v3 + n4v4 +.......... u rms = n1 + n2 + n3 + n4............... From kinetic theory of gas, urms =

or,

urms =

( M = N0 m and k =

= Boltzmann constant )

3. Most probable velocity( ump): It is the velocity possessed by maximum number of gas molecules at a given temperature. From kinetic theory of gas, ump =

or,

ump =

( M = N0 m and k =

= Boltzmann constant )

Relationship between the different kinds of velocity: urms : u : ump =

: :

= Or,

= 1.732 : 1.595 : 1.414 urms : u : ump = 1 : 0.92 : 0.816

: REAL GAS : What is ideal gas? Ans: Gasses which obey the ideal gas equation at all temperature and pressure are called ideal gas. What are real gas? Ans: The gasses which do not obey the ideal gas equation at all temperature and pressure are called real gasses. How do gasses deviate from ideal behavior? Or What is compressibility factor? Ans: Gas exhibit ideal behavior at low pressure and high temperature. The deviation of gasses from ideality can be measured in terms of the compressibility factor z. The compressibility factor is the ratio between the observed molar volume(V m) and ideal molar volume( Vmi).

ie.
but,

Vmi = z z

or, or, For n moles of gas, Vm = Or,

= =

z =

For ideal gas z = 1 and is independent of temperature and pressure . For real gasses z = f( P,T ). The figure below shows the graph between z and P at a constant temperature of 273K. At extremely low pressure the value of z for all gasses are close to unity, which implies that gasses behave almost ideally. At very high pressure, all the gasses have z more than unity indicating that the gasses are less compressible than an ideal gas. What is the relationship between compressibility factor and liquefaction of gas? Ans: Gasses with high compressibility factor are less compressible and are difficult to liquefy. Why do gasses deviate from ideal behavior? Ans: Gasses deviate from ideal behavior is attribute to two postulate which do not hold good under all condition( high pressure and low temperature). These two postulate are : 1. Gas molecules are regarded as point mass which means there volume is negligible compared to the volume occupied by the gas. 2. There is no intermolecular force between the gas molecule. Why do gasses deviate from ideality especially at low temperature and high pressure? Ans: The deviation of gas from ideal behavior is due to two postulate in the kinetic theory of gas. 1. Gas molecules are regarded as point mass which means there volume is negligible compared to the volume occupied by the gas. 2. There is no intermolecular force between the gas molecule. If the volume occupied by the gas is very high than volume occupied by the molecules can be neglected. On the other hand at high pressure and low temperature the gaseous volume is small, the volume occupied by the molecules cannot be neglected. Hence gasses deviate from ideality at high pressure and low temperature. What is Boyle temperature?

Ans: The temperature at which a particular gas obeys Boyles law at all range of temperature is called Boyle temperature( TB). Boyle temperature is characteristic of gas. For example the Boyle temperature for H2 is 117K while that of CH4 is 297K. van der Walls equation: By taking into account of intermolecular forces between the gas molecules and there volume, van der Wall modified the ideal gas equation by correcting the volume and pressure term. van der Walls equation for one mole gas is; (P + )( V nb ) = nRT

For one mole gas, (P + )( V b ) = RT

Constant a and b are called van der Walls constant and there value depends upon the nature of the gas. Physical significance of a and b: The value of a is a measure of the magnitude of the intermolecular forces between the gas molecules. Higher the value of a more compressible is the gas and easily liquefiable. The value of b is measure of the excluded volume ie. the volume not available for the gas molecules to move about. The numerical value of b is four timed the actual volume occupied by the gas molecules. Higher the value of b less compressible is the gas and difficult to liquify. Unit of a: We have, Or ,

= p
a =

If pressure is in atmosphere and volume in liter, a = atm.L2mol2 or atm.dm6mol2 ( 1L = dm3 ) In SI unit, pressure in Pa(Nm2) and volume in m3, a = (m3)2 mol2 Nm2 or, a = (m3)2 Nm4 mol2

Unit of b: We have. nb = v b =

( v = excluded volume )

Unit of b in Lmol1 or dm3 mol1or m3 mol1 Exercise: (a) Two gasses have the same a value but different values of b. Which woild be more compressible? Ans: The gas with smaller value of b will be more compressible and easy to liquefy. (b). The mass of He atom is twice the mass of H 2 molecule. At temp T, what is the relationship between the average kinetic energy of these gas molecule. Ans: Same, since the average kinetic energy of gas molecule depends upon the temperature and not the molecular mass.