STATES OF MATTER

Water can exist as ice, which is a solid; it can exist as liquid; or it can exist in the gaseous state as water vapour or steam Chemical properties of a substance do not change with the change of its physical state; nature of intermolecular forces, molecular interactions and effect of thermal energy on the motion of particles because a balance between these determines the state of a substance.

Threestatesis depictedas follows:

INTERMOLECULARFORCES Intermolecular forces are the forces of attraction and repulsion between interacting particles (atoms and molecules

Dispersion Forces or London Forces-- Atoms and non polar molecules are electrically symmetrical and have no dipole moment because their electronic charge cloud is symmetrically distributed. But a dipole may develop momentarily in such atoms and molecules. The intermolecular forces of attraction in between two temporary dipoles non polar substances is nown as London force or dispersion force.

 These forces are always attracti e and interaction ener!y is in ersely proportional to the si"th power of the distance between two interactin! particles !i.e., #/r$ where r is the distance between two particles". #hese forces wor at short distances !$%&& pm" and their magnitude depends on the polarisability of the particle.

Dipole% Dipole Forces

'ipole(dipole interactions occur between molecules that have permanent net dipoles between )Cl* molecules, +Cl, molecules, C-,Cl molecules and -Cl molecules. #he dipole ( dipole interactions are stronger than the .ondon forces. #he dipole(dipole interaction energy between stationary molecules is proportional to /0r, and for rotating molecules is proportional to /0r1, where r is the distance between the polar molecules.

Dipole % &nduced dipole

A dipole(induced dipole attraction is a wea attraction that results when a polar molecule induces a dipole in an atom or in a non polar molecule by disturbing the arrangement of electrons in the non(polar species. #he interaction energy is proportional to /0r1 where r is the distance between two molecules.

'ydro!en (ondin!
2n a molecule, whenever the hydrogen atom is directly lin ed to a highly electronegative atom !li e 3, 4 or 5", the shared pair of electron is pulled more towards this atom and it acquires a slight negative charge !d6" and the hydrogen atom acquires a slight positive !d(" charge. #here occurs a wea bond formation between the negative end of one molecule and the positive end of the other. #his bond is nown as a hydrogen bond, which is represented by dotted lines. 2t involves dipole(dipole interactions.

THEGASLAWS

E"periments of (oyle) in a *uantitati e manner pro e that !ases are hi!hly compressible because when a !i en mass of a !as is compressed) the same number of molecules occupy a smaller space+ This means that !ases become denser at hi!h pressure+ A relationship can be obtained between density and pressure of a !as by usin! (oyle,s law By definition, density 7d8 is related to the mass 7m8 and the volume 7V8 by the relation d9m0v. 2f we put value of V in this equation from Boyle8s law equation, we obtain the relationship.

#his shows that at a constant temperature, pressure is directly proportional to the density of a fixed mass of the gas.

Problem5.1 A balloon is filled with hydrogen at room temperature. It will burst if pressure exceeds 0.2 bar. If at 1 bar pressure the gas occupies 2.27 L volume, upto what volume can the balloon be expanded ? Solution According to Boyles Law p1V1 =p2V2 if p is 1 bar, V will be 2.27L
1 1

if p = 0.2 bar, then V =p V /P

2 2 1 1 2

:V =1 bar2.27L/0.2bar=11.35L Since balloon bursts at 0.2 bar pressure,the volume of balloon should be less than 11.35 L.

Each line of the volume vs temperature graph is called isobar.

All gases obey Charles8 law at very low pressures and high temperatures.

Problem5.2 On a ship sailing in pacific ocean where temperature is 23.4 C , a balloon is filled with 2 L air. What will be the volume of the balloon when the ship reaches Indian ocean, where temperature is 26.1C ? Solution V = 2L From Charles law T = (23.4 + 273)K = 296.4 K V /T =V /T T = 26.1 + 273 = 299.1 K :V =(V T )/T :V =2L 299.1K / 296.4K =2L 1.009 =2.018L
1 1 2 1 1 2 2 2 2 1 2 1

.ay Lussac/s Law 01ressure- Temperature Relationship2,

R =(10 Pa) (22.71 10 m )/(1mol) (273.15K) =8.314 Pa m k mol =8.314 X10 bar L K mol =8.314 JK mol
5 3 3 3 -1 -1 -2 -1 -1 -1 -1

At STP conditions used earlier (0 C and 1 atm pressure), value of R is 8.20578 X10 L atm K mol .
0 -2 -1 -1

Ideal gas equation is a relation between four variables and it describes the state of any gas, therefore, it is also called equation of state. Let us now go back to the ideal gas equation. This is the relationship for the simultaneous variation of the variables. If temperature, volume and pressure of a fixed amount of gas vary from T , V and p to T , V and p then we can write
1 1 1 2 2 2

p V /T and p V /T : p V /T = p V /T (5.19)
1 1 1 2 2 2 1 1 1 2 2 2

Problem 5.3 At 25C and 760 mm of Hg pressure a gas occupies 600 mL volume. What ill !e its pressure at a height here temperature is "0C and volume of the gas is 6#0 mL. Solution p" $ 760 mm Hg% &%su!'gt("$ 600 mL )" $ 25 * 27+ $ 2,- . &2 $ 6#0 mL and )2 $ "0 * 27+ $ 2-+. According to Com!ined gas la p" &"/)" $ p2 &2/)2 :p2$p" &")2/ &"/)2 :p2$0760 mm Hg120600 ml1202-+ .1/06#0 ml1202,- .1 $676.6 mm Hg

;ases are generally collected over water and therefore are moist. +ressure of dry gas can be calculated by subtracting vapour pressure of water from the total pressure of the moist gas which contains water vapours also. +ressure exerted by saturated water vapour is called aqueous tension

p'ry gas 9 p#otal< Aqueous tension !%.*="

Partial pressure in terms of mole fraction

1artial pressure in terms of mole fraction )uppose at the temperature #, three gases, enclosed in the volume V, exert partial pressure p/, p* and p, respectively. then,

here n/ n* and n, are number of moles of these gases. #hus, expression for total pressure will be

p#otal 9 p/ 6 p* 6 p,

4n dividing p/ by p

total

we get

here n 9 n/6n*6n,
x/ is called mole fraction of first gas. #hus,

p/ 9 x/ p

total

)imilarly for other two gases we can write p* 9 x* ptotal and p, 9 x, ptotal #hus a general equation can be written as

pi 9 xi ptotal

where pi and xi are partial pressure and mole fraction of ith gas respectively.

Problem 5.4 A neon3dio45gen mi4ture contains 70.6 g dio45gen and "67.5 g neon. 6f pressure of the mi4ture of gases in the c5linder is 25 !ar. What is the partial pressure of dio45gen and neon in the mi4ture 7 8um!er of moles of dio45gen $70.6g/+2gmol9" $ 2.2" mol 8um!er of moles of neon $"67.5g/20gmol9" $ -.+75 mol :ole fraction of dio45gen $ 2.2"/02.2" * -.+751 $ 2.2"/"0.5-5 $ 0.2" :ole fraction of neon $ -.+75/02.2"* -.+751 $ 0.7, Alternativel5% mole fraction of neon $ " ; 0.2" $ 0.7,

<artial pressure of a gas$ mole fraction 4 total pressure : <artial pressure of o45gen $ 0.2" 4 025 !ar1 $ 5.25 !ar <artial pressure of neon $ 0.7, 4 025 !ar1 $ ",.75 !ar

3&4ET&5 MOLE56LAR T'EOR7 OF .ASES

understand our o!servations. )he theor5 that attempts to elucidate the !ehaviour of gases is =no n as =inetic molecular theor5. Assumptions or postulates of the =inetic molecular theor5 of gases are given !elo . )hese postulates are related to atoms and molecules hich cannot !e seen% hence it is said to provide a microscopic model of gases. > ?ases consist of large num!er of identical particles 0atoms or molecules1 that are so small and so far apart on the average that the actual volume of the molecules is negligi!le in comparison to the empt5 space !et een them. )he5 are considered as point masses. )his assumption e4plains the great compressi!ilit5 of gases. > )here is no force of attraction !et een the particles of a gas at ordinar5 temperature and pressure. )he support for this assumption comes from the fact that gases e4pand and occup5 all the space availa!le to them. > <articles of a gas are al a5s in constant and random motion. 6f the particles ere at rest and occupied fi4ed positions% then a gas ould have had a fi4ed shape hich is not o!served. > <articles of a gas move in all possi!le directions in straight lines. @uring their random motion% the5 collide ith each other and ith the alls of the container. <ressure is e4erted !5 the gas as a result of collision of the particles ith the alls of the container. > Collisions of gas molecules are perfectl5 elastic. )his means that total energ5 of molecules !efore and after the collision remains same. )here ma5 !e e4change of energ5 !et een colliding molecules% their individual energies ma5 change% !ut the sum of their energies remains constant. 6f there ere loss of =inetic energ5% the motion of molecules ill stop and gases ill settle do n. )his is contrar5 to hat is actuall5 o!served. > At an5 particular time% different particles in the gas have different speeds and hence different =inetic energies. )his assumption is reasona!le !ecause as the particles collide% e e4pect their speed to change. Aven if initial speed of all the particles as same% the molecular collisions ill disrupt this uniformit5. ConseBuentl5 the particles must have different speeds% hich go on changing constantl5. 6t is possi!le to sho that though the individual speeds are changing% the distri!ution of speeds remains constant at a particular temperature. > 6f a molecule has varia!le speed% then it must have a varia!le =inetic energ5. Cnder these circumstances% e can tal= onl5 a!out average =inetic energ5. 6n =inetic theor5 it is assumed that average =inetic energ5 of the gas molecules is directl5 proportional to the a!solute temperature. 6t is seen that on heating a gas at constant volume% the pressure increases. Dn heating the gas% =inetic energ5 of the particles increases and these stri=e the alls of the container more freBuentl5 thus e4erting more pressure. .inetic theor5 of gases allo s us to derive theoreticall5% all the gas la s studied in the previous sections. Calculations and predictions !ased on =inetic theor5 of gases agree ver5 ell ith the e4perimental o!servations and thus esta!lish the correctness of this model.

EXERCISES 5.1 What will be the minimum pressure required to compress 500 dm of air at 1 bar to 200 dm at 30C?
3 3

5.2 A vessel of 120 mL capacity contains a certain amount of gas at 35 C and 1.2 bar pressure. The gas is transferred to another vessel of volume 180 mL at 35 C. What would be its pressure? 5.3 Using the equation of state pV=nRT; show that at a given temperature density of a gas is proportional to gas pressure p. 5.4 At 0C, the density of a certain oxide of a gas at 2 bar is same as that of dinitrogen at 5 bar. What is the molecular mass of the oxide? 5.5 Pressure of 1 g of an ideal gas A at 27 C is found to be 2 bar. When 2 g of another ideal gas B is introduced in the same flask at same temperature the pressure becomes 3 bar. Find a relationship

between their molecular masses 5.7 What will be the pressure exerted by a mixture of 3.2 g of methane and 4.4 g of carbon dioxide contained in a 9 dm flask at 27 C ?
3

5.8 What will be the pressure of the gaseous mixture when 0.5 L of H at 0.8 bar and 2.0 L of dioxygen at 0.7 bar are introduced in a 1L vessel at 27C?
2

5.9 Density of a gas is found to be 5.46 g/dm at 27 C at 2 bar pressure. What will be its density at STP?
3

5.10 34.05 mL of phosphorus vapour weighs 0.0625 g at 546 C and 0.1 bar pressure. What is the molar mass of phosphorus? 5.7 What will be the pressure exerted by a mixture of 3.2 g of methane and 4.4 g of carbon dioxide contained in a 9 dm flask at 27 C ?
3

5.8 What will be the pressure of the gaseous mixture when 0.5 L of H at 0.8 bar and 2.0 L of dioxygen at 0.7 bar are introduced in a 1L vessel at 27C?
2

5.9 Density of a gas is found to be 5.46 g/dm at 27 C at 2 bar pressure. What will be its density at STP?
3

5.10 34.05 mL of phosphorus vapour weighs 0.0625 g at 546 C and 0.1 bar pressure. What is the molar mass of phosphorus? 5.11 A student forgot to add the reaction mixture to the round bottomed flask at 27 C but instead he/she placed the flask on the flame. After a lapse of time, he realized his mistake, and using a pyrometer he found the temperature of the flask was 477 C. What fraction of air would have been expelled out? 5.12 Calculate the temperature of 4.0 mol of a gas occupying 5 dm at 3.32 bar. (R = 0.083 bar dm K mol ).
3 3 -1 -1

5.13 Calculate the total number of electrons present in 1.4 g of dinitrogen gas. 5.14 How much time would it take to distribute one Avogadro number of wheat grains, if 1010 grains are distributed each second ? 5.15 Calculate the total pressure in a mixture of 8 g of dioxygen and 4 g of dihydrogen confined in a vessel of 1 dm3 at 27C. R = 0.083 bar dm K mol .
3 -1 -1

5.16 Pay load is defined as the difference between the mass of displaced air and the mass of the balloon. Calculate the pay load when a balloon of radius 10 m, mass 100 kg is filled with helium at 1.66 bar at 27C. (Density of air = 1.2 kg m and R = 0.083 bar dm K mol ).
-3 3 -1 -1

5.17 Calculate the volume occupied by 8.8 g of CO2 at 31.1C and 1 bar pressure. R = 0.083 bar L K mol .
-1

-1

5.18 2.9 g of a gas at 95 C occupied the same volume as 0.184 g of dihydrogen at 17 C, at the same pressure. What is the molar mass of the gas?

5.19 A mixture of dihydrogen and dioxygen at one bar pressure contains 20% by weight of dihydrogen. Calculate the partial pressure of dihydrogen. 5.20 What would be the SI unit for the quantity pV T /n ?
2 2

5.21 In terms of Charles law explain why -273 C is the lowest possible temperature. 5.22 Critical temperature for carbon dioxide and methane are 31.1 C and -81.9 C respectively. Which of these has stronger intermolecular forces and why? 5.23 Explain the physical significance of v 5.1 2.5 bar 5.2 0.8 bar 5.4 70 g/mol 5.5 M = 4M
B

5.6 202.5 mL 5.7 8.314 x 10 Pa

4

5.8 1.8 bar 5.9 3g/dm

3

5.10 1247.7 g 5.11 3/5 5.12 50 K 5.13 4.2154 x 10 electrons

23

5.14 1.90956 x 10 year

6

5.15 56.025 bar 5.16 3811.1 kg 5.17 5.05 L 5.18 40 g mol 5.19 0.8 bar
&ndash;1

an der Waals parameters.