# Solutions & Colligative Properties_(Lecture Notes)

September 22, 2017 | Author: mrdldwivedi | Category: Solubility, Distillation, Solution, Chemical Process Engineering, Physics & Mathematics

#### Description

Topics to be covered:

Lecture # 1 Section (A) : 1.

General Introduction

2.

Types of solutions 2.1 Solids solutions (solid solvent) 2.2 Liquid solutions (liquid solvent) 2.2.1 Types of liquid-liquid solution (liquid solute-liquid solvent) (a) completely miscible liquids. (b) completely immiscible liquids. (c) partially miscible liquids. 2.3 Gaseous solutions (gaseous solvent)

Section (B) : 3.

Expressing cocentration of solutions Various types of concentration terms 3.1 Percentage (%) composition

w v %, (b) %, w v Strength of solution Molarity Molality Mole fraction Parts per million (a)

3.2 3.3 3.4 3.5 3.6

(c)

w % v

Lecture # 2 Section (C) : 4.

Solutions of solids in liquids 4.1 Solubility of solids in liquids 4.2 Factors affecting the solubility of solids in liquids 4.2.1 Nature of solute 4.2.2 Nature of solvent 4.2.3 Effect of temperature (solubility curves) 4.2.4 Effect of pressure (no effect)

5.

Solutions of gases in liquids 5.1 Solubility of gases in liquids 5.2 Factors affecting the solubility of a gas in liquids 5.2.1 Nature of gas. 5.2.2 Nature of solvent. 5.2.3 Effect of temperature 5.2.4 Effect of pressure (Henry’s law)

Section (D) : 6.

Vapour pressure of liquid-liquid solution 6.1 Vapour pressure 6.2 Factors affecting vapour pressure 6.2.1 Nature of liquid 6.2.2 Temperature (Clausius-clapeyron equation) 6.2.3 Surface area of liquid

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Lecture # 3 6.3

Vapour pressure of liquid-liquid solutions (volatile solute) Raoult’s law for volatile solutes. 6.3.1 Statement 6.3.2 Derivation of Raoult’s law (all forms) y1 y2 1 = 0 + 0 p1 p2 P Graphical representation of Raoult’s law

y1P = x1p1º ; P = x1 p1º + x2p2º ; 6.3.3 Section (E) : 7.1

Application of Raoult’s law for volatile solute 7.1.1 Fractional distillation

7.2

Phase diagram (Bubble and dew points)

7.3

Ideal & non-ideal solution. 7.3.1 Properties of ideal solution. 7.3.2 Properties of non-ideal solution. 7.3.3 Examples of positive deviation and negative deviation from Raoult’s law.

7.4

Azeotropic or constant boiling mixture. 7.4.1 Azeotropes (Maximum & minimum boiling azeotropic mixture). 7.4.2 Explanation of azeotropes with graphs.

7.5

Vapour pressure of completely immiscible liquids.

Lecture # 4 Section (F) : 8.1

Introduction to colligative properties. 8.1.1 Types of colligative properties. 8.1.2 Van’t Hoff’s factor (a) When electrolyte dissociates. (b) Electrolyte associates.

8.2

Vapour pressure of solutions of solids in liquids and Raoult’s law. 8.2.1 Relative lowering in vapour pressure. 8.2.2 Raoult’s law as a special case of Henry’s law. 8.2.3 Determination of molecular masses of solute from lowering of vapour pressure. 8.2.4 Measurement of RLVP (Ostwald-Walker dynamic method).

Lecture # 5 Section (G) : 8.3

Elevation of boiling point. 8.3.1 Concept of boiling point. 8.3.2 Expression for the elevation in boiling point. 8.3.3 Determination of molecular mass of solute. 8.3.4 Calculation of molal elevation constant from enthalpy of vaporisation.

[2]

8.4

Depression in freezing point. 8.4.1 General discussion. 8.4.2 Expression for the depression in freezing point. 8.4.3 Calculation of molecualr mass of solute. 8.4.4 Calculation of molal depression constant from enthalpy of fusion. 8.4.5 Application of depression in freezing point. 8.4.6 Rast method.

Lecture # 6 Section (H) : 8.5

Osmotic pressure. 8.5.1 Definition of osmosis. 8.5.2 Osmotic pressure. 8.5.3 Expression for the osmotic pressure. 8.5.4 Experimental measurement of osmotic pressure. 8.5.5 Isotonic solution. 8.5.6 Determination of molecular mass (polymer and colloidal solution). 8.5.7 Explanation of some phenomena (biological) on the basis of osmosis. 8.5.8 Osmotic pressure of mixture of two or more than two solution.

[3]

LECTURE # 1 (1) General Introduction : In normal life we rarely come across pure substances. Most of these are mixtures containing two or more pure substances. Their utility or importance in life depends on their composition. For example, the properties of brass (mixture of copper and zinc) are quite different from those of German silver (mixture of copper, zinc and nickel) or bronze (mixture of copper and tin); 1 part per million (ppm) of fluoride ions in water prevents tooth decay, while 1.5 ppm causes the tooth to become mottled and high concentrations of fluoride ions can be poisonous (for example, sodium fluoride is used in rat poison); intravenous injections are always dissolved in water containing salts at particular ionic concentrations that match with blood plasma concentrations and so on. In this Unit, we will consider mostly liquid solutions and their formation. This will be followed by studying the properties of the solutions, like vapour pressure and colligative properties. We will begin with types of solutions and then various alternatives in which concentrations of a solute can be expressed in liquid solution. (2) Types of solutions : Solution : A solution is a homogeneous mixture of two or more chemically non-reacting substances whose composition can be varied within certain limits. Solvent : A solvent is that component of the solution which is present in the largest amount by mass. A solvent determines the physical state of solution in which it exists. Solute : One or more components present in the solution other than the solvent are called solutes. Binary solution : A solution containing only one solute dissolved in given solvent is called Binary Solution. Types of Solutions : Type of solution

Solute

Solvent

Common Examples

Gaseous Solutions

Gas

Gas

Mixture of oxygen and nitrogen gases

Liquid

Gas

Chloroform mixed with nitrogen gas

Solid

Gas

Camphor in nitrogen gas

Gas

Liquid

Oxygen dissolved in water

Liquid

Liquid

Ethanol dissolved in water

Solid

Liquid

Glucose dissolved in water

Gas

Solid

Liquid

Solid

Amalgam of mercury with sodium

Solid

Solid

Copper dissolved in gold

Liquid Solutions

Solid Solutions

Types of liquid-liquid solution (liquid solute-liquid solvent) : (a) Completely miscible liquids : When both the liquids are polar (e.g., ethyl alcohol and water) or both are non-polar (e.g., benzene and hexane), they mix completely in all proportions to form a homogeneous mixture. They are said to be completely miscible. (b) Completely immiscible liquids : When one liquid is polar and the other is non polar, e.g., benzene and water or cyclohexane and water etc., they do not mix at all and form separate layers. They are said to be completely immiscible. (c) Partially miscible liquids : When two liquids are not exactly similar in nature and also not completely dissimilar in nature, e.g., ether and water, they dissolve in each other to a limitied extent only. They are said to be partially miscible. Simillarly, we have phenol and water or nitrobenzene and hexane.

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{Though i am defining all the concentration terms once again in first lecture but try and give minimum time in the class on this section and try to move directly to second lecture you should move according to the class requirement} Concentration Terms : 1.

% Concentration

weight of solute (gm) (a) % w/w = weight of solution (gm) = wt of solute/100 gm of solution. % wt/wt (w/w) does not depends on temp. Ex.

10% w/w urea sol.

= 10 gm of urea is present in 100 gm of solution. = 10 gm of urea is present in 90 gm of water.

(b) % wt/vol. (w/v) % w/v = no. of gm of solute/100 mL of solution

gm of solutes % w/v = vol. of solution in mL  100 Ex.

10% (w/v) urea solution. = 10 gm of urea is present in 100 mL of solution. But not 10 gm of urea present in 90 ml of water for dilute solution : vol. solution = vol. solvent. (c) % v/v : If both solute & solvent are liquids = volume in (mL) of solute per 100 mL of soln.

Ex.

10% v/v alchol ethanol aq solution = 10 ml of ethanol in 100 ml of sol.  10 ml of C2H5OH in 90 ml of H2O

2.

Strength of solution in gm/L wt. of solute (in gms) per litre (1000 mL) of solution.

Ex.

10% (w/v) sucrose soln, then specify its conc. in gm/L 100 mL .......... 10 gm 10  1000 = 100 gm/L 100 If we have 6% w/w urea soln with density 1.060 gm/mL then calculate its strength in g/L. 6 gm in 100 gm solution.

 1000 mL ........

Ex.

6 gm in

100 mL 1.060

100 mL  6 gm. 1.060 6 x 1.060 x 1000 = 10.6 x 6 = 63.6  1000 mL = 100

3.

Molarity (Depends on temp.) = No. of moles of solute per litre of soln. Soluite moles = n Solvent moles = N

n 1000 W M = V (in L ) =   x V in (mL ) M no. of moles of solute = molarity x volume ( in L) no. of m. moles of solute = molarity x volume ( in mL) If V1mL of C1M solution is mixed with V2 mL of C2M solution (same substance or solute)  Cf (V1+V2) = C1V1 + C2V2

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 C1V1  C 2 V2  Total moles  = Cf =  V  V Total volume 1 2   Ex.

If 20 ml of 0.5 M Na2SO4 is mixed with 50 ml of 0.2 M H2SO4 & 30 ml of 0.4 M Al2(SO4)3 solution calculate. [Na+], [H+], [SO42–], [Al3+]. Assuming 100% dissociation moles = 10 m. moles of Na2SO4 volume  20 m. moles of Na+

=

 [Na+] =

(ii)

[H+] = ? 10 m. moles H2SO4 20 m. moles H+ [H+] =

4.

20 = 0.2 M 100

(P)

20 = 0.2 M 100

(iii)

SO42– =

(iv)

Al3+ =

10  10  36 56 = = 0.56 M 100 100

24 = 0.24 M 100

Molality (Does not depends on temp.) = No. of moles of solute per 1 kg(1000 gm) of solvent of w gm of solute (Molar mass = m gm/mole) is dissolved in 'W' of solvent.

1000 w molality =   x W (gm) M moles 1000 molality = solvent W (gm) Derive a relationship between moalaity & molarity of a solution in which w gm of solute of molar mass m gm/mol is dissolved in W gm solvent & density of resulting solution = 'd' gm/ml. say 1 L solution taken, mass of 1 lit solution = (1000 d) gm moles of solute = (molarity) mass of solute = (molarity) x m mass of solvent = W = 1000 d – (molarity) x m (molarity )  1000  molality = (no. of moles of solte) 1000 d  molarity  M.Wt

Ex.

5.

Calculate molarity of 1.2 M H2SO4 solution if its  = 1.4 gm/mL 1.2  1000 Molarity = 1000  1.4  1.2  98 = 0.865 Normality No. of equivalents per litre of solution no. of equivalent s of solute = volume of solution (in L ) no. of equivalents = normality  volume (in L) (Normality = n  molarity) 'n' factor (i) For oxides/reducing agents : no. of e– involved in ox/red half per mole of O.A./Red. 5e– + 8H+ + MnO4–  Mn2+ + H2O (ii) For acid/ base reactions : no. of H+ ions displaced/ OH– ions displaced per mole of acid/ base. (iii) For salt:

[6]

n = Total charge on cations. or total charge on anions 6.

Simple salts

Mole Fraction

moles of solute n Xsolute = total moles in solutions = nN moles of solvent nN + XSolvent = 1

XSolvent = Xsolute Ex.

If we have 10 molal urea soln calculate (i) Mole faction of urea in this solution & also calculate % w/w of urea. (ii) MW = 60 10 moles urea in 1000 gm of water X urea =

10 10 1000 = 65.55 10  18

10  60 x 100% 10  60  1000  = 1.5 gm/mL  molarity = % w/v & strength in gm/L of the solution 10 moles urea in 1000gm H2O = (1000 + 600) gm of solution

% w/w weight of urea = 10 x 60 = 600 = (iii)

=

1600 mL of solution 1 .5

10  1.5 150 x 1000 = = 9.3 M 1600 16 strength in gm/L = (9.3 x 60) gm/L

molarity =

600  1.5 60 15 225 x 100% = = = 56.25% 1600 16 4 Note : For dil. aq. solution molality  molarity

% w/v =

molarity  1000 molality = 1000  d  molarity  m  (1 gm/ml) 7. ppm (Parts Per Million). (a)

wt. of solute (in gm) ppm (w/w) = wt. of solution (in gm) x 106 = 1 million

(b)

wt. of solute (in gm) ppm (w/v) = vol. of solution (in mL ) x 106

(c)

moles of solute ppm (moles/moles) = moles of solution x 106

Ex.

Calculate molarity of CaCO3(aq.) soln which has conc of CaCO3 = 200 ppm.

Ex.

Molality of urea soln. which has X urea = 0.2

n = 0.2 nN 0.2 moles of urea in 0.8 moles water

0 .2 250 125 x 1000 = = 0.8  18 18 9

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LECTURE # 2 Solubility : Solubility of a substance is its maximum amount that can be dissolved in a specified amount of solvent at a specified temperature. It depends upon the nature of solute and solvent as well as temperature and pressure. Let us consider the effect of these factors in solution of a solid or a gas in a liquid. Solubility of a solid in a liquid : Every solid does not dissolve in a given liquid. While sodium chloride and sugar dissolve readily in water, naphthalene and anthracene do not. On the other hand, naphthalene and anthracene dissolve readily in benzene but sodium chloride and sugar do not. It is observed that polar solutes dissolve in polar solvents and non polar solutes in non-polar solvents. In general, a solute dissolves in a solvent if the intermolecular interactions are similar in the two or we may say like dissolves like. When a solid solute is added to the solvent, some solute dissolves and its concentration increases in solution. This process is known as dissolution. Some solute particles in solution collide with the solid solute particles and get separated out of solution. This process is known as crystallisation. A stage is reached when the two processes occur at the same rate. Under such conditions, number of solute particles going into solution will be equal to the solute particles separating out and a state of dynamic equilibrium is reached. Solute + Solvent Solution At this stage the concentration of solute in solution will remain constant under the given conditions, i.e., temperature and pressure. Similar process is followed when gases are dissolved in liquid solvents. Such a solution in which no more solute can be dissolved at the same temperature and pressure is called a saturated solution. An unsaturated solution is one in which more solute can be dissolved at the same temperature. The solution which is in dynamic equilibrium with undissolved solute is the saturated solution and contains the maximum amount of solute dissolved in a given amount of solvent. Thus, the concentration of solute in such a solution is its solubility. Earlier we have observed that solubility of one substance into another depends on the nature of the substances. In addition to these variables, two other parameters, i.e., temperature and pressure also control this phenomenon. Effect of temperature The solubility of a solid in a liquid is significantly affected by temperature changes. Consider the equilibrium represented by equation. This, being dynamic equilibrium, must follow Le Chateliers Principle. In general, if in a nearly saturated solution, the dissolution process is endothermic (sol H > 0), the solubility should increase with rise in temperature and if it is exothermic (sol H > 0) the solubility should decrease. These trends are also observed experimentally. Effect of pressure Pressure does not have any significant effect on solubility of solids in liquids. It is so because solids and liquids are highly incompressible and practically remain unaffected by changes in pressure.

[8]

Solubility of solids in solution vs T

Henry Law : Henry law deal with effect of pressure on the solubility of gas. Statement : The solubility of a gas in a liquid at a given temperature is directly proportional to the pressure at which it is dissolved. Let X = Mole fraction of gas at a given temperature as a measure of its solubility. p = Partial pressure gas in equilibrium with the solution. Then according to Henry's law. Xp or pX or p = KH X where KH = Henry law constant. Solubility of gases in solution vs T (P=constant)

[9]

Note : (i) If a mixture of gases is brought in contact with solvent each constituent gas dissolves in proportion to its partial pressure. It means Henry's law applies to each gas independent of the pressure of other gas. (ii) Henry's law can also apply by expression the solubility of the gas in terms of mass per unit volume. Mass of the gas dissolved per unit volume of a solvent at a given temperature is directly proportional to the pressure of a gas in equilibrium with the solution. m  p, m = K × p where, m = mass of gas dissolved in unit volume of solvent. p = pressure of gas in equilibrium with solution. Where K is the constant of proportional that depends on nature of gas, temperature & unit of pressure. Characteristics of Henry law constant (KH). (i) unit same as those of pressure torr or Kbar. (ii) Different gas have different value of KH . (iii) The KH value of a gas is different in different solvents and it increase with the increase in temperature. (iv) Higher the value of KH of a gas lower will be its solubility. Plot of p Vs X is a straight line passing through the origin with slop equal to KH

Plot of p Vs X for solution of HCl in cyclohexane. Limitation of Henry's law : Henry law valid only following condition. (i) The pressure of gas is not too high. (ii) The temperature is not too low. (iii) The gas should not go any chemical reaction with the solvent. (iv) The gas should not undergo dissociation in solution. Application of Henry's law : Several application in biological and industrial phenomena. (i) To increase the solubility of CO2 in soft drinks and soda water the bottle is sealed under high pressure. (ii) Scuba divers must cope with high concentrations of dissolved gases while breathing air at high pressure underwater. Increased pressure increases the solubility of atmosphere gases in blood. When the divers come towards surface, the pressure gradually decreased. The release the dissolved gases and leads to the formation of bubbles of nitrogen in the blood. This blocks capillaries and creates a medical condition known as bends, which are painful and dangerous to life. To avoid bends, as well as, the toxic effects of high concentrations of nitrogen in the blood, the tanks used by scuba divers are filled with air diluted with helium (11.7% helium, 56.2% nitrogen and 32.1% oxygen). (iii) At high altitudes the partial pressure of oxygen is less than that at the ground level. This leads to low concentrations of oxygen in the blood and tissues of people living at high altitudes or climbers. Low blood oxygen causes climbers to become weak and unable to think clearly, symptoms of a condition known as anoxia. Effect of temperature : Solubility of gases in liquids decreases with rise in temperature. When dissolved, the gas molecules are present in liquid phase and the process of dissolution can be considered similar to condensation and heat

[10]

is evolved in this process. We have learnt that dissolution process involves dynamic equilibrium and thus must follow Le Chatelier's principle. As dissolution is an exothermic process, the solubility should decrease with increase of temperature. Note : KH values for both N2 and O2 increase with increase of temperature indicating that the solubility of gases increases with decrease of temperature. It is due to this reason that aquatic spcies are more comfortable in cold wasters rather than warm water. Ex.

The Henry's law constant for the solubility of N2 gas in water at 298 K is 1.0 × 105 atm. The mole fraction of N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water of 298 K and 5 atm pressure is : [JEE - 2009] (A*) 4 × 10–4 (B) 4.0 × 10–5 (C) 5.0 × 10–4 (D) 4.0 × 10–6

Sol.

PN = KH × x N2 2

x N2 =

1 105

× 0.8 × 5 = 4 × 10–5 per mole

In 10 mole solubility is 4 × 10–4 .

Vapour Pressure

Vacuum

Vacuum

liquid (10gm)

t=0

(Imagine no liquid molecule exist in vapour phase)

finally

Vacuum h

liquid (5 gm) at equilibrium The pressure exerted by vapours of the liquid when equilibrium is established b/w vapours & the liquid. say 5 gm liquid left at teq At eq. : the rate of evaporation = rate of condense H2 O () H2 O (g) Kp = PH2O(g) eq. Hence V.P is equilibrium constant (KP) of the reaction. liquid vapours.  Since vapour pressure is an equilibrium constant so its value is dependent only on temp. for a particular liquid not only on the amount of liquid taken on surface area of the liquid or on volume or shape of the container.

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Important Points related to vapour pressure : C-1

The partial press of vapours in equilibrium with pure solid or pure liquid at a given temperature. At eq. the rate of evaporation = rate of condensation e.g. H2O(l) H2O(g) eq Kp = pH2O,g

C-2

C-3

(a)

Vap pressure of water is called aq. tension

(b)

Relative Humidity (R.H.) =

Partial pressure of water vap. v.p. of water at same temp. × 100

(a) Boiling point :- The temperature at which the bulk of liquid. may convert to vapour. on suppying heat at a given pressure. (b) At boiling pt. Pº = Pext (c) At normal boiling pt Pº = 1atm

C-4(a) Since vapour press is an eqlibrium constant. so it's value is dependent only on (a) temp. for a particular liquid (b) Nature of liquid. C-4 (b) It does not depend on (i) Amt. of liquid (ii) surface area of liquid (iii) volume or shape of container Moreover, we can say that it is a characteristic const. C-5. C-5.1 5.2

The numerical value of liquid's vap. pressure depends on the magnitude of the intermolecular forces present & on temperature. The smaller the intermolecular fores, higher the vap. pressure becuase loosely held molecules escape more easily. The higher the temperature , higher the vap. pressure because larger fraction of molecules have sufficient kinetic energy to escape. (Acc. to maxwell distribution law)

C-7

V.P. represents the highest partial pressure which may be exerted by vapurs of liquid at that temperature.

C-8

If it's partial pressure is increased beyond this value (Pº) its vapours begin to condense till their partial pressre becomes equal to the vapur pressure.

C-9

If the partial pressure of vapour is less than v.p. of liquid, the liquid (if present) will vaporize till (a) its v.p. is attained or (b) the liquid completely gets vaporized

C-10

If a volatile solid/ liquid is brought in contact with a gas (or vaccuum), vapours of that solid/ liquid occupy the gas phase till the gas phase becomes saturated with that solid /liquid vapours.

Ex.

The vapor pressure of water at 80º C is 355 torr. A 100 ml vessel contained watersaturated oxygen at 80º C, the total gas pressure being 760 torr. The contents of the vessel were pumped into a 50.0 ml, vessel at the same temperature. What were the partial pressures of oxygen and of water vapor, what was the total pressure in the final equilibrated state ? Neglect the volume of any water which might condense.

Ans.

PO2 = 810mm Hg, PH2O = 355 mm Hg , Ptotalal = 1165 mm Hg

Sol.

In 100 ml vessel which contained water - saturated oxygen, the pressure of O2 gas = 760 – 355 = 405 torr when the contents of this vessel were pumped into 50 ml vessel, at the same temperature, the pressure of oxygen gets doubled i.e. PO2 = 810 torr.. But pressure of water vapour will remain constant, as some vapour in this 50 ml vessel, gets condensed. So PH2O = 355 torr & Total pressure = 810 + 355 = 1165 torr.

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LECTURE # 3 Vapour Pressure of liquid-liquid solution : VOLATILE SOLVENT  Liq. solution SOLUTIONS CONTAINING   VOLATILE SOLUTE  Liq. solution

Mix of 2 volatile liquids Raoult's law ( for volatile Liq. Mixture )

A x

x

x x x

x

B

x x

A+B XA {mole factions of A & B in liq. solution} XB let A, B be to two volatite liq. Partial pressure of A = PA & According to Raoult's law (experimentally ) PA  XA PA = XAPAº PAº – V.P. of pure liq. A = ( constant at a particular tamp ) PB  XB.

Similarly.

if PAº > PBº

PB = XBPBº (V.P. of pure liq. B)

 

A is more volatile than B B.P. of A < B.P. of B

 According to Dalton's law PT = PA + PB = XAPA0 + XBPB0 xA' = mole fraction of A in vapour above the liquid / solution. xB' = mole fraction of B Daltion's law for gaseous mix PA = XA' PT Raoult's law when liq & vap. in equilibrium PA = XAPAº XA' PT = XA PAº PB = XB' PT = XBPBº XA + XB = 1 =

X A ' PT PA0

+

XB ' PT PB0

xA ' xB ' 1 PT = PA º + PB º

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Graphical Representation : PA= XAPAº

&

PT

PB = XB PBº

PT = XAPAº + XB PBº

PB,º

PT = XAPAº + (1 – XA) PBº = ( PAº – PBº ) XA + PB0

PA º

PA PB,

PT = (1 – XB) PAº + XBPBº = ( PBº – PAº ) XB + PA0 eg. PT = 150 + 200Xben.

XA= 0 XB= 1

A more volatile than B PAº > PBº PT = PA + PB.

XA= 1 XB= 0

Non - deal solutions : Ideal solutions ( mixtures ) :

+ ve deviation

– ve deviation

1. Which follow Raoul'ts law at all temp. Which do not follow Rault's law Which do not obey Raoult's law. (i) PT,exp > ( XAPºA + XBPBº ) & at all compositions. (i) PT exp < xApº + xBpºB PT = XAPAº + XB PBº A    A A    A (ii) B    B > A ---- B (ii) B    B > A ------ B. 2. Forces of attraction b/w the liq. strong force of altraction.  molecules are exactly same. (iii) Hmix = –ve Weaker force of attraction A ------ A = A -------- B = B ----- B. (iv) Vmix = –ve(1L+1L 2L ) 3. Hmix = 0 (vi) Gmix = –ve (v) Smix = +ve eg. H2O + HCOOH 4. Vmix = 0 (vi) Gmix = –ve. H2O + CH3COOH eg. H2O + CH3OH. H2O + HNO3 5. Smix = + ve as for process to H2O + C2H5OH CHCl3 + CH3OCH3 proceed. C2H5OH + hexane CH3 Cl C2H5OH + cyclohexane. 6. Gmix = – ve CHCl3 + CCl4  dipole dipole interac C=O H C Cl eg. (1 ) Benzene + Toluene. tion becomes weak Cl CH3 (2) Hexane + heptane. (3) C2H5Br + C2H5.

P

P

P0A > P0B

XA = 0 XB = 1 + ve deviation

XA = 1 XB = 0

P0A > P0B

xB = 1 XA = 0 – ve deviation

X A= 1 XB = 0

+ ve deviation

[14]

azeotropic (constant boiling mix/Composition)  Minimum boiling azeotropic mix.

– ve deviation

t azeotropic composition max. boiling azeotropic mix

Ex.

An equimolar mix of benzene & toluene is prepared the total V.P. of this mix as a fraction of mole fraction of benzene is found to be PT = 200 + 400 Xben. (a) Calculate composition of vapours of this mix. [ Assume that the no. of moles going into vapour phase is negligible in comparsion to no. of moles present in liq. phase ]. (b) f the vapour above liq in part A are collected & are condensed into a new liqiuid calculate composition of vapours of this new liq.

Sol.

P0Beazene= 600 mm of Hg

(a)

P0Toloune = 200 mm of Hg

1 1 × 600 + × 200 = 400 mm of Hg 2 2 Pbenz =Xben ' Pºben = X'benPT. PT =

x'benzene =

1/ 2  600 3 = = 75% 400 4

x'Toloune =

1 = 25% 4

75% 25%

(b)

PT =

condensate ( Liq. formed after condensation of vapours.

3 1 × 600 + × 200 = 500  4 4

distillate ( rem. liq.)

x1ben =

3 / 4  600 = 0.9 = 90% 500

X'Tol = 0.1 = 10% This process is known as fractional distillation.

[15]

Ex.

Ans. Sol.

(a)

A liquid mixture of benzene and toluene is composed of 1 mol of benzene and 1 mol of toluene. If the pressure over the mixture at 300K is reduced, at what pressure does the first bubble form? (b) What is the composition of the first bubble formed. (c) If the pressure is reduced further, at what pressure does the last trace of liquid disappear? (d) What is the composition of the last drop of liquid? (e) What will be the pressure, composition of the liquid and the composition of vapour, when 1 mol of the mixture has been vaporized? Given PT0 = 40mmHg, PB0 = 100mmHg (a) 70 mmHg, (b) xb = 5/7 (c) P = 400/7 = 57.14 mm (a) P = XAPA0 + XBPB0 = 0.5 x 40 + 0.5 x 100 = 70 0.5 x 40 2 = 70 7 (c) at last trace of liquid

5 7 YA = 0.5

(b) YA =

YB =

YB = 0.5

YA YB 0 .5 0 .5 1 = 0 + 0 = + PA PB 40 100 P

P=

(d) YA =

(e)

400 7

YA PA0 P

 0.5 =

X A 40 5 XA = 400 / 7 7

1-x

x

B=x

T=1-x

XB =

2 7

P = 40 (1 – x) + 100 x

YA YA 100 x  (1  x )40 x 1 x 1 1 = 0 + P  = + = 40 x 100 PA 40 100 P P B So

p2 = 40 x 100 p = 20 10

20 10 = 40 (1 – x) + 100x = 40 + 60x x=

20 10  10 = 60

10  2 3

Immiscible Liquids : Completely Immiscible Liquids : Steam Distillation It is probably true that no two liquids are absolutely insoluble in each other, but with certain pairs, eg., mercury and water and carbon disulfide and water, the mutual solubility is so small that the liquids may be regarded as virtually immiscible. For systems of this type, each liquid exerts its own vapor pressure, independent of the other, and the total vapor pressure is the sum of the separate vapour pressures of the two components in the pure state at the given temperature. The composition of the vapor can be readily calculated by assuming that the gas laws are obeyed; the number of moles of each constituent in the vapor will then be proportional to its partial pressure, that is to say, to the vapor pressure of the substance in the pure state. If p 0A and pB0 are the vapor pressures of the pure liquids A and B, respectively, at the given temperature, and n’A and n’B are the numbers of moles of each present in the vapor, the total pressure P and the same temperature is given by P = P  p 0A  pB0 ,

(1)

[16]

and the composition of the vapor by

n' A p 0A  n'B pB0

(2)

To express the ratio of A to B in the vapor in terms of the actual weights wA and wB, the numbers of moles must be multiplied by the respective molecular weights MA and MB ; hence,

wA wB

n' A MA p 0A MA  0 n'B MB pBMB

(3)

A system of two immiscible liquids will boil, that is, distill freely, when the total vapor pressure P is equal to the atmospheric pressure. The boiling point of the mixture is thus lower than that of either constituent. Further, since the total vapor pressure is independent of the relative amounts of the two liquids, the boiling point, and hence the composition of the vapor and distillate, will remain constant as long as the two layers are present. The properties just described are utilized in the process of steam distillation, whereby a substance that is immiscible, or almost immiscible, with water, and that has a relatively high boiling point, can be distilled at a much lower temperature by passing steam through it. The same result should, theoretically, be obtained by boiling a mixture of water and the particular immiscible substance, but by bubbling steam through the latter the system is kept agitated, and equilibrium is attained between the vapour and the two liquids. The mixture distills freely when the total pressure of the two components is equal to that of the atmosphere. It is seen that chlorobenzene, which has a normal boiling point of 132ºC, can be distilled with steam at a temperature about 40º lower, the distillate containing over 70 percent of the organic compound. An examination of the calculation shows that the high proportion by weight of chlorobenzene in the steam distillate is due largely to the high molecular weight of this substance, viz., 112.5 as compared with that of water. In addition this case is a particularly favorable one because chlorbenzene has a relatively high vapor pressure in the region of 90º to 100ºC. In order that a liquid may be distilled efficiently in steam, it should therefore be immiscible with water, it should have a high molecular weight, and its vapor pressure should be appreciable in the vicinity of 100ºC. A liquid which is partially miscible with water, such as aniline, may be effectively distilled in steam, provided the solubility is not very great. In calculating the composition of the distillate, however, the pressures p 0A and pB0 in equation (3) would have to be replaced by the actual partial pressures. Attention may be called to the fact that equation (3) can be employed to determine the approximate molecular weight of a substance that is almost immiscible with water. This can be done provided the composition of the steam distillate and the vapor pressures of the two components are known.

Immiscible Liquids : 1.

It is used to purely an organic liquid from impurity.

2.

When two liquids are mixed in such a way that they do not mix at all then (i) Ptotal = PA + PB (ii) PA = PA0 XA XA = 1 PA = PA0 (iii) PB = PB0 XB XB = 1 PB = PB0 0 A

0 B

(iv) Ptotal = P + P PA0 =

(v)

PA0 PB0

nA = n B

(vi)

PA0 PB0

W A MB M A WB

n A RT nBRT ; PB0 = V V

[17]

TA

TB

Tsoln. B.P. of solution is less than the individual B.P.’s of both the liquids.

LECTURE # 4 Introduction to Colligative properties & constitutional properties : Colligative : The properties of the solution which are dependent only on the total no. of particles or total conc. of particles in the solution & are not dependent on the nature of particle i.e. shape, size, neutral /charge etc. of the particles. Constitutional Properties : Properties which are dependent on nature of particles are constitutional properties like electrical conductence. There are 4 colligative properties of solution  P   1. Relative lowering in vapour pressere   P 

2. Elevation in b.p. (T b) 3. Depression in freezing pt. (T f) 4. Osmotic pressure

Van’t Hoff Factor : Abnormal Colligative Properties : If solute gets associated or dissociated in solution then experimentable / observed / actual value of colligative property will be diff. from theoretically predicted value so it is also known as abnormal colligative property. This abnornality can be calculated in terms of vont. hoff factor.

i =

exp/ observed / actual / abnormal value of colligativ e property Theoritica l value of colligativ e property exp . / observed no. of particles / conc. Theoritica l no. of particles

Theoritica l mass of subs tan ce = exp erimental molar mass of the subs tan ce i > 1 dissociation i < 1 association i=

 exp .  theor

 = iCRT  = (i1C1 + i2C2 + i3C3.....) RT

Relation between i &  (degree of dissociation) : Let the electrolyte be Ax . By AxBy (aq.)  xAy+ + yBx–

[18]

t=0 teq

C C(1 – )

0 0 xC yC

 C – C + xC + yC = c [1 + ( x+y –1) ]. = c [1 + ( n –1) ]. n=x+y = no. of particles in which 1 molecules of electrolyte dissociates c[1  (n  1)] i= c i = 1 + ( n – 1)  e.g.

NaCl (100% ionise), i = 2. ; BaCl2 (100% ionise), i = 3. ; K4[Fe(CN)6] (75% ionise), i = 4.

Relation b/w degree of association  & i. t=0 teq

nA C

A n. 0



C n

C ( 1– )

 C – C +

C n

1   C [ 1 +  n  1  ]   1  i = 1 +   1  n 

dimerise n = 2 ; trimerise n = 3 ; tetramerise n = 4. e.g.

CH3COOH 100% dimerise in benzene, i =

1 1 ; C6H5COOH 100% dimerise in benzene, i = 2 2

Relative lowering in vapour pressure (RLVP) : Vapour Pressure of a solutions Vapour Pressure of a solutions of a non volatile solute ( solid solute ) is always found to be less than the vapour pressure of pure solvent . Reason : Some of the solute molecules will occupy some surface area of the solutions so tendency of the solute particles to go into the vapour phase is slightly decreased hence Ps

P

solvent

solution

Ps < P

[19]

PS < P Lowering in VP = P – PS

= P

P P Raoult's law : – ( For non – volatile solutes ) Experimentally relative lowering in V.P = mole fraction of the non volatile solute in solutions. relative lowering in

VP =

RLVP

=

P - Ps n = XSolute = P nN

P nN N P - Ps = n = 1+ n

P - P  Ps Ps P – 1 = = P - Ps P - Ps P - Ps

N = n

P - Ps n Ps = N

P - Ps w M Ps = m × W =

M w M w 1000 × × 1000 = × × 1000 m W m W 1000

P - Ps M Ps = ( molality ) × 1000

(M = molar mass of solvent)

If solute gets associated or dissociated

P - Ps i.n = Ps N P - Ps M = i × (molality) × Ps 1000 Ex.

Calculate wt of urea which must be dissolved in 400 gm of water so final solutions has V.P. 2% less than V.P. of pure water : let V.P be V. of water P0 – Ps = .02 V Ps = 0.98 V

0.02 0.98

w= Ex.

=

18 w × 60 400

;

where w = weight of urea.

2  60  400 gm. 18  98

10 gm of a solute is dissolved in 80 gm of acctone V.P. of this sol = 271 mm of Hg. If V.P. of pure acctone is 283 mm of Hg. Calculate molar mass of solute.

P - Ps w M Ps = m × W

[20]

58 283 - 271 10 = × 80 271 m

m = 163 gm/mol. Ex.

V.P. of solute containing 6 gm of non volatile solute in 180 gm of water is 20 Torr/mm of Hg. If 1 mole of water is further added in to the V.P. increses by 0.02. Torr calculate V.P of pure water & molecular wt. of non volatile solute.

P - Ps w M Ps = m × W

P - 20 18 6 = × 20 180 m P - 20.02 18 6 = × 20.02 198 m

P = 20.22 Torr. m = 54 gm/mol.

Ex.

What is the final volume of both container. Sol.

i1C1 = i2C2 0.1 2 0.1 1 = . 100  x 100 – x

200 – 2x = 100 + x. x = 33.3 ml. Ex.

If 0.1 M solutions of K4 [ Fe ( CN ) 6 ] is prepared at 300 K then its density = 1.2 gm/mL . If solute is 50% dissociated calculate P of solutions if P of pure water = 25 mm of Hg. (K = 39, Fe = 56)

P - Ps w M Ps = i m × W P - Ps im  M Ps = 1000 3  0.1 1000   18  =  1000  1 . 2 – 1 . 2  368   1000

P –3 Ps = 1 + 7.12 × 10 Ps = 24.82 mm of Hg p = 25 – 24.82 = 0.18 mm of Hg Ex.

(Barium ions) Ba2+ ions, CN– & Co2+ ions from a water soluble complex with Ba2+ ions as free cations for a

[21]

Sol.

0.01 M solution of this complex. O.P. = 0.984 atm & degree of dissociation = 75%. Then find coordination number of Co2+ ion in this complex (T = 300 K, R = 0.082 L atm. mol–1 k–1) Say C.N. = x 0.984 = i CRT 0.984 = i 0.01 × 0.082 × 300 = i × 0.246 i = 4 = 1 + (n –1)   n=5 Ba[Co(CN)x ]–(x – 2) Ba(x – 2) [Co(CN)x)2 x–2+2=5 x=5  CN = 5  Ba3[Co(CN)5)2 can also have Ans. as Ba4[Co(CN)5].

Ostwald–Walker Method : Experimental or lab determination of

dry air

P P or P P s

Ps

P anhydrous CaCl2 (dehydrating agent)

solution

solvent

1.

Initially note down the Wts. of the solution set, solvent set containers & of dehyehating agent before start of experiment.

2.

Loss of wt of solution containers  Ps. Loss of in wt of solvent containers  (P – Ps) gain in wt of dehydriating agent  P.

P  Ps loss in wt. of solvent = Ps loss in wt. of solution loss is wt. of solvent P  Ps = gain is wt. of dehydratin g agent P B.

Dry air was passed through a solution of 5 gm of a solute in 80 gm of water & then it is passed through pure water loss in wt. of solution was 2.50 gm & that of pure solvent was 0.04 gm. Calculate M.W. of solute.

P  Ps loss in wt. of solvent Ps = loss in wt. of solution P  Ps 0.04 = Ps 2.50 =

5 18  M 80

M = 70 gmole–1.

[22]

Ex.

If same volume solution of different solute is used then what is order of (a) vapour pressure (b) moles of solute (c) molar mass of solute. Ans.

PA  1 gm. ; PC – PB  1 gm ; PC > PA > PB ;

PA – PB  0.5 gm, PB  0.5 gm. PC  1.5 gm. nC < nA < nB . ; MC > MA > MB.

LECTURE # 5 Third colligative property : 3.

Elevation in Boiling point (Tb) Boiling point of a Liq. : The temprature at which vapour pressure of a liquid becomes equal to the external pressure present at the surface of the liquid is called b.p of liquid at that pressure. if Pext = 1 atm = 760 mm of Hg then it is called normal b.p. of liq. (Tb). H2O() H2O(g) H = +ve Kp = PH2O( g)/ eq.  K p2  ln  K  p1

 H  1 1      R  T1 T2  

 P2  ln   =  P1 

 H vap.   1 1    R  T  T  2   1

(Claussius – Clapeyron equation)

P

T

Boiling pt of any solution : Since V.P. of solution is smaller then V.P. of pure solvent at any temp. hence to make it equal to Pext. we have to increase the temp. of solution by greater amount in comparision to pure solvent.

Pext.

P Ps Hvap. of solvent = Hvapour solution

[23]

As only solvent particles are going into vapours.  Ts > T

S =

H T

Hvapour Svapour =

Tbp

H Svapour solvent = T b,solvent

H Svapour solution = T b, solution

Svapour

of solvent

> Svapour of solution.

Tb, solvent Tb, solution Due to presence of solute, it is difficult to vapourise the solution (so R.L.V.P occur), it is difficult to boil (so elevation in boiling point occur), it is difficult to freeze (so depression in freezing point occur). This diagram is related to boiling point elevation and freezing point depression of solutions is taken from 'MCMURRY FAY CHEMISTRY' for details see chapter -11 page no. 450.

1 atm

Pressure (atm)

Liquid

Psolv

Solid

Psoln Gas fpsolv

fpsoln Tf

bpsolv

bpsoln Tb

Temperature (ºC)

Phase diagram for a pure solvent (red line) and a solution of a nonvolatile solute (green line). Because the vapor pressure of the solution is lower than that of the pure solvent at a given temperature, the temperature at which the vapor pressure reaches atmospheric pressure is higher for the solution than for the solvent. Thus, the boiling point of the solution is higher point of the solution is higher by an amount Tb . Further

[24]

more, because the liquid / vapor phase transition line is lower for the solution than for the solvent, the triple point temperature Tt is lower and the solid/ liquid phase transition line is shifted to a lower temperature. As a result, the freezing point of the solution is lower than that of the pure solvent by an amount Tf . Graphical :

A B C

P

t E en 1 v l n o o s uti 2 D l so tion u l so

Tb Tb1 Tb2 T If solution are dilute then BE & CD can be approximated as st. lines.  ABE & ACD will be similar. AB AE  AC AD

Tb1 P1  Tb 2 P2 

Tb  P

using Raoult’s law :

n w M P   . .P P nN M W  Tb 

w M . .P m W

 w 1000   M  .P      W   1000  M

 Tb = Kb × molality Kb is dependent on property of solvent and known as molal elevation constant of solvent Kb = elevation in bp of 1 molal solution.

Tb K Units : molality  mol / kg = K kg mol–1

Using thermodynamics 2

Kb = 

RTb 1000  L vap

LVap – is cal/gm or J/gm R = 2 cal mol–1 cal–1 or 8.314 J .... Tb = b.p. of liq. (in kelvin) Kb = K kg mol–1

[25]

2

RTb M Also Kb = 1000  H vap

Hvap – molar enthalpy of vaporisation

 H vap Lvap =  M 

   

e.g. Calculate Kb of water if Lvap = 540 Cal/gm Tb = 100ºC 

Kb =

2  373  373 = K kg mol–1 = 0.52 K k/gm 1000  540

if solute gets associated/dissociated t = i × Kb × molality Ex.

A solution of 122 gm of benzoic acid is 1000 gm of benzene shows a b.p. elevation of 1.4º. Assuming that solute is dimerized to the extent of 80 percent (80ºC) calculate normal b.p. of H benzene. given molar enthalpy of vap. of benzine = 7.8 Kcal/mole. H H   1  122  1000   1   1 0 . 8   Tb – Ti = × Kb   122  1000   n  H H 

1  Kb   0.8 2 

H

Tb – Ti = Kb × 0.6 2

Kb =

RTb 1000  L vap.

Kb =

2  Tb  78 1000  7.8  1000

2

1.4 =

0.4  2 10

5

Tb

2

Tb = 418.33 K Ex.

Sol.

1 Lit. of aq. solution of urea having density = 1.060 gm/mL is found to have Tb = 0.5ºC, If temp. of this solution increase to 101.5ºC then calculate amount of water which must have gone is vapour state upto this pt. given Kb = 0.5 K kg mol–1 for water mass of solution = 1.060 × 103 = 1060 gm 0.5 = 0.5 ×

1060 M 1060 60

 1060 × 60 = M 1 Lit solution = 1060 gm (Mass of water) i = 1000 gm urea = 60 gm Tb = (molality)i × Kb (Molality)i 

W water =

60 1000 3 = 60  W water

1000 gm. 3

[26]

mass of water vaporised = 1000 –

=

1000 3

2000 gm 3

= 666.67 gm

Fourth colligative property : 4.

Depression in freezing pt (Tb) Freezing point : Temprature at which vapour pressure of solid becomes equal to v.p of liq. is called freezing pt of liq. or melting pt. of solid.

vacuum Hsub = + ve Hsub > Hvap.

ice cube Hsub = Hfusion + Hvap. H2O(s)

H2O (g)

Kp = PH2O (g) /eq. = V.P. of solid

P

olv d (s i u Liq

A

d soli E D

) ent

solution 1 solution 2

B C

0ºC

T

For - dil. solutions BE & CD can be assumed to be straight lines.  using Similar S Tf  P  Tf = Kf . Molality Kf = molal depression constant. 2

2

RTf RTf M = = 1000  L fusion 1000  Hfusion for water Tf = 273 K & LFusion = 80 cal / gm

[27]

Kf = *

2  273  273 = 1.86 K kg mol–1 1000  80

At freezing pt or below it only solvent molecules will freeze not solute molecules (solid will be of pure solvent) SFusion =

Hfusion Tf P

SSoution > Ssolvent freezing point of solution < freezing point of solvent These 4 colligative properties are calculated only for solution containing non volatile solutes. Ex.

0.1M urea 0.1M NaCl 0.1M BaCl2 , , (A) (B) (C)

order of  order of R.L.V.P order of V.P order of TB order of TB of solution order of TF order of TF of solution Ex.

Sol.

C > B > A. C > B > A. A > B > C. C > B > A. C > B > A. C > B > A. A > B > C.

Van’t Hoff factors of aqueous solutions of X, Y, Z are 1.8, 0.8 and 2.5. Hence, their (assume equal concentrations in all three cases) (A) b.p. : X < Y < Z (B*) f. p. Z < X < Y (C) osmotic pressure : X = Y = Z (D) v. p. : Y < X < Z As van’t Hoff factor increases RLVP increases i.e., V.P. decreases y > x > z Elevation in b.p. increases i.e., b.p. increases y < x < z Depresion in f.p increases i.e., f.p decreases y>x>z Osmotic pressure increases so y < x < z.

Ex.

1000 gm H2O have 0.1 mole urea and its freezing point is – 0.2ºC and now it is freezed upto – 2ºC then how much amount of ice will form.

Sol.

It is assume that solute do not freeze and do not vapourise

[28]

TF = 0.2 = Kf 0.1 × 1000

.......(i)

1000

TF = 2 = Kf

0 .1 × 1000 wt. of solvent

.......(ii)

on dividing

wt. of solvent 0 .2 = . 1000 2

weight of remaining H2O is 100 gm and weight of ice is 900 gm. Ex. Sol.

If boiling point of an aqueous solution is 100.1ºC. What is its freezing point? Given latent heat of fusion and vaporization of water are 80 cal g–1 and 540 cal g–1 respectively. For a given aqueous solution Tb = Kb × molality Tf = Kf × molality 1000 lf K b' Tb RTb2 = = × ' RTf2 . Tf 1000 lv Kf

Tb2  lf Tb Tf = T 2  lv f

Tb = 100 + 273 = 373 K. Tf = 0 + 273 = 273 K. lf = 80 cal g–1. lv = 540 cal g–1. 0. 1 373  373  80 Tf = 273  273  540 .

Tf = 0.362. Tf = 0.0 – 0.362.= – 0.362ºC.

  Ex.

Sol.

A 0.001 molal solution of a complex reprsented as Pt(NH3)4Cl4 in water had a freezing point depression of 0.0054ºC. Given Kƒ for H2O = 1.86 molality–1. Assuming 100% ionisation of the complex, write the ionisation nature and formula of complex. Let n atoms of Cl be the acting as ligand. Then formula of complex and its ionisation is : [Pt(NH3)4Cln]Cl(4 – n)  [Pt(NH3)4Cln]+(4 – n) + (4 – n) Cl– 1 0 0 0 1 (4 – n) Thus particles after dissocation = 4 – n + 1 = 5 – n and therefore, van't Hoff factor (i) = 5 – n Now Tƒ = K'ƒ × molality × van't Hoff factor 0.0054 = 1.86 × 0.001 × (5 – n)  n = 2.1  2 (integer value) Thus complex and its ionisation is :

Ex.

Sol.

[Pt(NH3)4Cl2]Cl2  [Pt(NH3)4Cl2]2+ + 2Cl– Depression of freezing point of 0.01 molal aq. CH3COOH solution is 0.02046°. 1 molal urea solution freezes at – 1.86°C. Assuming molality equal to molarity, pH of CH3COOH solution is : (A) 2 (B*) 3 (C) 3.2 (D) 4.2 For urea Tf = kf × m

or

kf =

Tf 1.86 = = 1.86 m 1

Now for CH3COOH Tf = i kf m 0.02046 = 1.1 1.86  0.01

so

i=

Now so

i=1+  = 1.1 – 1 = 0.1

[29]

Now

CH3COOH C C – C

CH3COO– 0 C

+

H+ 0 C

[H+] = C = 0.01 × 0.1 = 0.001 so

pH = 3.

LECTURE # 6 Osmosis & Osmotic pressure : Osmosis & Diffusion Diffusion : Spontaneous flow of particles from high conc. region to lower conc. region.

H2O

Ex.

Blue

Cu2+

CuSO4

Saturated (Solution)blue

Uniform

Ex.

Conclusion : After some time in (A) grape or egg will shrink and in (B) grape or egg will swell. Ex.

In which soluton side complex [Cu(NH3)4]2+ will form and deep blue colour will obtain.

Ans. In neither of side colour complex will form. Osmosis : The spontaneous flow of solvent particles from solvent side to soultion side or from solution of low conc. side to solution of high conc. side through a semipermeable membrane = (SPM) SPM : A membrane which allows only solvent particles to more across it. (a) Natural : Semi permeable membrane

[30]

(i) (b)

Animal/plant cell membrane formed just below the outer skins. Artificial membranes also : A copper ferrocyanide. Cu2[Fe(CN)6] & Silicate of Ni, Fe, Co can act as SPM.

Osmotic Pressure :

h --------------------------Solvent Solution SPM

The equilibrium hydrostatic pressure developed by solution column when it is seperated from solvent by semipermeable membrane is called O.P. of the solution.  = gh  = density of soln. g = acc. due to gravity h = eq. height 1 atm = 1.013 x 105 N/m 2 Pext.

Solution

C1

Solvent

SPM

C2

Definition : The ext pressure which must be applied on solution side to stop the process of osmosis is called osmotic pressure of the of the solution. C1 > C2 particle movement. Pext. = (1 – 2) Pext. must be applied on the higher conc. side. Remarks : If the pressure applied on the soln side is more than osmotic pressure of the solution then the solvent particles will move from solution to solvent side. This process is reverse osmosis. Berkely : Hartely device/method uses the above pr. to measure O.P. Vont – Hoff Formula (For calculation of O.P.)   concentration (molarity) T  = CST S = ideal soln. constant = 8.314 J mol–1 K–1 (exp value) = R (ideal gas) constant

 = atm.

C – mol/lit. R – 0.082 lit.atm. mol–1 K–1 T – kelvin

n RT (just like ideal gas equation) V In ideal solns solute particles can be assumed to be moving randomly without any interactions.  C = total conc. of all types of particles.  = CRT =

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= C1 + C2 + C3 + s.................

(n1  n 2  n3  .........) V If V1 mL of C1 ion + V2 mL of C2 conc. are mixed. =

Ex.

C1V1  C 2 V2 V1  V2

Cf =

 1 

1 = C1RT, C1 =  RT     2 

2 = C2RT, C2 =  RT   

 C1V1  C 2 V2   RT  =  V  V T 1 2   1V1  2 V2  =  V  V   

1

2

Type of solutions : (a) Isotonic solution 2 solutions having same O.P. 1 = 2 (at same temp.) (b) Hyper tonic Ist If 1 > 2 solution is hypertonic solution w.r.t. 2nd solution. (c) Hypotonic 2nd solution is hypotonic w.r.t. Ist solution.

Conclusion :

Ex.1

Ex.2

Pressure is applied on the hypertonic solution to stop the flow of solvent partices, this pressure become equal to (2 – 1) and if hypotonic solution is replaced by pure solvent then pressure becomes equal to 2. Calculate osmotic pressure of 0.1 M urea aq. solution at 300 K , R = 0.082 lit atm K–1  = CRT  = 0.1 x 0.082 x 300  = 2.46 atm Osmotic pressure of very dilute solns is also quite significant so its measurement in lab is very easy. If 10 gm of an unknown substance (non-electrolyic) is dissolved to make 500 mL of soln then OP at 300 K is observed to be 1.23 atm find m.wt. ? 10  1000 1.23 = x 0.0832 x 300 M  500 M=

Ex.3

20 0.0832 x x 300 1.23 100

 400 gm/mol

If 6 gm of urea, 18 gm glucose & 34.2 gm sucrose is dissolved to make 500 mL of a soln at 300 K calculate  M.W. of urea = 60 gm , Glucose = 180gm , SUcrose = 342 gm  = C x 0.082 x 300

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=

0.3  1000  0.082  300 500

 14.76 atm Ex.4

If 200 mL of 0.1 M urea soln is mixed with 300 mL of 0.2 M Glucose soln. at 300 K calculate  0.02 moles urea 0.06 moles Glucose

 =

0.08  0.083  300 0. 5

or

 C1V1  C 2 V2   RT  =  V  V T 1 2  

= 3.94 atm Ex.5

If an urea (aq) solution at 500K has O.P. = 2.05 atm. & glucose solution at 300 K has OP = 1.23 atm. If 200 ml of Ist solutions & 400 ml of 2nd soln are mixed at 400 K then cal. O.P. of resulting solution as 400 K (assume molarity is not dependent on temp.) Curea =

2.05 = 0.05  200 mL R  500

Cglucose =

1.23  400 mL R  300

F = (CF × RT)  2.05   1.23     200 moles     400 moles  R 500    R  300  CF = 600 mL

F =

(0.05 )200  (0.05 )400 (0.05 )  600 x 0.083 x 400 = x 0.083 x 400 600 600

= 0.05 x 0.083 x 400 = 20 x 0.083 = 1.66 atm.

LECTURE # 7 Ex.

When reaction is not taking.

Ex.

Calculate  of a solutions having 0.1 M NaCl & 0.2 M Na2SO4 and 0.5 HA (weak acid which is 20% dissociation solutions at 300 K)  = ( 0.2 + 0.6 ) RT + i3 C3 RT i3 = 1+(1).2 =1.2 T  [ 0.8 + 0.6 ] RT = ( 1.4 × 0.083 × 300 ) = 1.162 × 30 = 34.86 atm

Ex.

If 0.04 M Na2SO4 solutions at 300 K is found to be isotonic with 0.05 M NaCl (100 % disscociation) solutions calculate degree of disscociation of sodium sulphate. i C1 RT = i2 C2 RT [ 1+(2)  ] 0.042 = 2 × 1+2 =

0.05 2

5 –1 2

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2  =  = Ex.

3 2

3 × 100 = 75 %. 4

If 6 gm of CH3 COOH is dissolved in benzene to make 1 litre at 300 K  of solutions is found to be 1.64 atm. If it is known that CH3COOH in benzene forms a dimer.

CH3

O

O

C

C CH3 O

O

H

H O

O O

C

C O

O

H

Calculate degree of association of acetic acid in benzene 1  i = 1 +   1 . n  1  1.64 = 0.0823 × 300 × [ 1 +   1  ] n 

1.64 = 0.0823 × 300 [1 –

 ] 0.1 2

1.64 2- = 00.823  30 2 1.64 2- = 2.46 2

4 = 6 – 3 3 = 2 = Ex. Ex. Ans.

2 3

When reaction is taking place. If 200 ml of 0.2 M BaCl2 solutions is mixed with 500 ml of 0.1 M Na2SO4 solutions. Calculate of resulting solutions. BaCl2 + Na2SO4  BaSO4 + 2 NaCl 0.04 moles 0.05 0 0 m moles of Ba +2 = 40 Cl – = 80 So42– = 50 Na+ = 100 +2 2– Ba + SO4  BaSO4 40 50 0 Ba2+ SO42– 0 10

=

BaSO4  not affect Colligative properties 40

(80  10  100 ) × 0.082 × 300 atm. 700

= 6.685 atm.

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Other method : BaCl2 + Na2SO4  BaSO4 + 2 NaCl 0.04 moles 0.05 0 0 0 0.01 Not effect 0.08 0.01 0 .7

Not effect

0.08 0 .7

 = (i1C1 + i2C2) RT. = (3 × Ex.

0.01 0.08 +2× ) 0.082 × 300. = 6.685 atm. 0 .7 0 .7

If 200 ml of 0.2 m HgCl2 solution is added to 800 ml of 0.5 M KI (100% dissciated) solution. Assuming that the following complex formation taken place to 100% extent. Hg 2++ 4– [HgI4 ] 2– (Complexes are always soluble) 0.04 0.4 Calculate O.P. of resulting initially solution at 300K initially  400 millimoles K+  400 millimoles I+ Hg2+  40 millimoles Cl –  80 millimoles Hg2+ + 4I –  [ HgI4 ]2–  t 40 400 0 tf 0 240 40 finally = K+ + I– + Cl– + [ HgI4 ]2– = 400 + 240 + 80 + 40 =

760 × 0.0823 × 300 1000

 = 18.69 atm. Other method : HgCl2 + 4KI 40 400 0 400 –160 240 1000

40 1000

K[HgI4] + 2KCl. 0 0 40 80 80 1000

 = (i1C1 + i2C2 + i3C3) RT. = (0.24 × 2 + 3 × 0.04 + 0.08 × 2) 0.082 × 300. = 18.69 atm.

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