Department of Chemistry

CH-207 PHYSICAL CHEMISTRY PRACTICALS I

I. THERMOCHEMISTRY Water Equivalent of Calorimeter Determination of Heat of Ionisation Integral and Differential Heat of Solution

II. ADSORPTION Verification of Freundlich and Langmuir adsorption isotherms

III. PHASE DIAGRAMS Simple Eutectic - Napthalene Biphenyl System Partially miscible liquids Phenol - Water system Effect of electrolytes and non electrolytes on CST (+2 expt) Three component systems (+4 expt)

IV. PARTITION COEFFICIENTS Iodine between carbon tetra chloride and water Benzoic acid between benzene and water.(Graphically also) Equilibrium constant, KI + I2KI2

V. VISCOMETRY Verification of Kendalls equation Composition determination

VII. RASTS METHOD (+2 expt) VIII. HEAT OF SOLUTION BY SOLUBILITY DETERMINATION

Department of Chemistry

THERMOCHEMISTRY
___________________________________________________________________

Experiment 1: Water Equivalent of Calorimeter

Aim:

___________________________________________________________________ To determine the water equivalent of the given calorimeter Principle: When a known weight of hot water is added to known volume of the cold water at room temperature, the calorimeter and the cold water will take up the heat from the hot water. The heat gained by the cold water and calorimeter will be equal to heat lost by hot water added. Using this principle the water equivalent of the calorimeter can be determined. Requirements: Calorimeter, Sensitive thermometer. Procedure: A known volume (100ml) of distilled water is taken in a beaker and its temperature at an interval of 1 minute is recorded. Some water (more than 100ml) is heated to about 90C and then 100ml of this hot water is poured in to calorimeter. As soon as hot water is added to calorimeter, the calorimeter is closed and its content is stirred with the stirrer attached. Simultaneously the temperature of calorimeter is recorded at an interval of 1min till it attains a constant value. After getting 3 consecutive constant temperature values for hot water, 100ml of cold water is added to calorimeter. Soon after the addition the calorimeter lid is closed and it is stirred continuously. Simultaneously the temperature of calorimeter is recorded at an interval of every 30 seconds till a constant value is achieved. The constant temperature is noted and calculations are made. Observation: Time
(min)

Temperature of Cold water Hot water

Time
(sec)

Temperature after mixing C

1 2 3 4 5

30 60 90 120 150 180 210 240 270 300 330 360

Department of Chemistry
Calculations: Weight of Cold water Contant temperature for cold water Weight of Hot water Contant temperature for Hot water Resultant temperature Heat gained by water and calorimeter Heat lost by hot water Heat gained = Heat lost (e + W1)(t3 t1) = W2(t2 t3) e = [W2(t2 t3)/ (t3 t1) ] - W2 Result: ___________________________________________________________________ = W1 = T1C = W2 = T2C = T3C = (e + W1)(t3 t1) = W2(t2 t3)

If e is the water equivalent of the calorimeter,

Experiment 2: Determination of Heat of Ionisation ___________________________________________________________________

Aim: To determine the heat of ionisation of a weak acid with sodium hydroxide. Principle: Weak acids do not ionise completely in dilute solutions much, when they are neutralised by strong alkalies. This heat of neutralisation will be accompanied by the heat of ionisation also.(ie) If either the acid or base is weak or if both are weak, the heat of neutralisation is not constant quantity equal to 13.7Kcal but less than this value. In such a case neutralisation process consist not only in the union of H+ or OH- but the ionisation of weak acid or weak base. The measured heat of neutralisation will be equal to the sum of heat evolved in the union of H + and OHand the heat of weak acid or weak base. A known volume of HCl solution of exactly known concentration is allowed to react completely with a strong alkali in dilute solution and the rise in temperature is determined. Knowing the water equivalent of calorimeter, mass of acid and alkali taken the amount of heat liberated can be measured. With the known volume and concentration of acid solution the heat of neutralisation can be calculated. If Q is the quantity of heat evolved when Vml of HCl of concentration Cgm equivalent/litre is neutralised completely then: Heat of Neutralisation = 1000 x Q VxC Requirements: Calorimeter, Sensitive thermometer, NaOH, weak acid

Department of Chemistry
Procedure: The calorimeter is taken and its water equivalent is determined. Now using the same calorimeter the temperature for 100ml 1N NaOH solution is determined at an interval of 1min till a constant temperature is noted. The alkali is then removed from the calorimeter to beaker and washed. Next transfer 100ml of weak acid into the calorimeter and its temperature at an interval of 1min is determined till a constant reading is noted. After getting 3 consecutive constant readings, the 100ml 1N NaOH kept in beaker is poured into the calorimeter having 100ml of weak acid in it. The mixture is stirred well continuously and temperature is noted at an interval of 30 seconds till 3 consecutive constant values are obtained. The constant value is noted. Observation: (i)Standardisation of NaOH solution Volume of NaOH (ml) Burette Reading Initial Final Volume of Acid (ml)

V1N1 = V2N2 Normality of Stock Solution = Time (sec) Temperature of Acid Alkali Mixture

Mass of NaOH, M1 Temperature of NaOH, T1 Mass of weak acid, M2 Temperature of weak acid, T2 Mean Temprature, T3 Final Temperature, T4

= = = = = (T1 + T2)/2 = = (200 + C)(T3 T2)cals = Q x 10 cals

Heat evolved during neutralisation,Q Heat of neutralisation Therefore, Heat of ionisation = Precaution:

The volume and concentration of acid solution should be exactly known. The alkali solution should be slightly more concentrated. Result:

Department of Chemistry
___________________________________________________________________

Experiment 3: Integral and Differential Heat of solution

Aim:

___________________________________________________________________ To determine the integral and differential heats of the solution of KCl. Principle: Integral heat of solution at a particular concentration is the heat change when 1 mole of solute is dissolved in pure solvent to produce a solution of the given concentration. From the heat change for the dissolution of m moles of the solute, the heat change per mole can be determined. When heats of solution at different solutions are plotted against the number of moles of the solute added, the slope of the curve gives the differential heat of solution. The differential heat of solution may be defined as the heat of solution of a mole of solute in such a large quantity of solution of known concentration that addition of one mole of the solute does not change the concentration appreciably. Requirements: Calorimeter, Sensitive thermometer, KCl, Procedure: 100ml of water is taken in the Dewar flask. The temperature of water noted. About 2gm of KCl (weighted accurately) is added into the flask and dissolved with stirring. The resultant temperature is noted. The experiment is repeated with 4,6, 8 gms of KCl and dissolving in 100ml of water each time. The integral heat of solution is calculated using the relation. Integral heat of solution = (C + W + m) T x M/m. Where C is the water equivalent, W is the wt of water, m the wt of KCl added and M the molecular weight of KCl. Observation: Molecular mass of KCl, M = Water equivalent of calorimeter, C = Weight of water, W = Weight of KCl Temperature Integral heat of water

Result:

Department of Chemistry

ADSORPTION
___________________________________________________________________

Experiment 1: Adsorption of Oxalic acid on Charcoal

Aim:

___________________________________________________________________

To determine the adsorption isotherm of oxalic acid from aqueous solution by activated charcoal and to calculate the unknown concentration of oxalic acid. Principle: The extend of adsorption depends on temperature i.e. decreases with increase of temperature, for the process absorption is an exothermic process. However at a fixed temperature for a given amount of adsorbent, the amount of adsorption increases with concentration of adsorbent (in solution) or pressure. An expression representing the variation of the amount adsorbed with the equilibrium pressure or concentration of the adsorbate or concentration at a fixed temperature is known as adsorbtion isotherm. An empirical equation relating the amount of adsorption to the concentration of the adsorbate or to the pressure of the gas at a fixed temperature is known as Freundlich Adsorption Isotherm. When Charcoal powder is added to a solution of oxalic acid, a fraction of the acid will be adsorbed by charcoal .According to Freundlich, x/m = kP1/ x/m = kc1 / n Where, x is the number of moles of oxalic acid absorbed by m grams of charcoal and c is the equilibrium concentration of the acid, k and n being constants, former depends upon the nature of both adsorbent and adsorbate and is greater than unity. The plot of x/m values against corresponding pressure or concentrations is practically a straight line at low concentration, indicating thereby the direct proportionality of the amount of adsorption with pressure for low values. Taking logarithms of above equations we get:log x/m = log k + 1/ log P log x/m = log k + 1/n log c Therefore the plot of log(x/m) against log c should be straight line with slope equal to 1/n and intercept equal to log k. Using the above expression the strength of the given oxalic acid solution can be found out .It should be noted that such a graph is linear for a narrow range of concentration or pressure. Requirements: N/2 oxalic acid, activated charcoal, N/10 KMnO4, five labeled conical flasks Procedure: Take five labeled conical flasks with stoppers and burette out 20,30,40,50 and 60 ml of N/2 oxalic acid in each of the flask to 100ml with water. Accurately weighed amounts (1-2grams) of activated charcoal are added in each. The flasks are shaken well for about 15 minutes. The supernatant liquid of each of the bottle is filtered through small dry filter papers of equal size (use different filter papers for different bottles) into properly labeled dry flasks. 5-10 ml of the initial filtrate is rejected and the remaining filtrate is collected in separate conical flasks. 20ml of the filtrate in each

Department of Chemistry
conical flask is titrated against standard N/10 KMnO4.The experiment is repeated with the unknown acid and its concentration is calculated. In order to test the validity of Freundlich adsorption isotherm, plot log x/m values against log ce and by putting ce /(x/m) values versus ce .A linear plot obtained shows the applicability of isotherm. Calculate the constants a and b from the slope and the intercept on the ordinate axis. Precautions: Fresh activated charcoal should be used and the filter paper should be dry. The temperature of each flask should be constant since the rate of adsorption increases with temperature.

Observations: Weight of Oxalic Acid,W = Normality of Oxalic acid ,N1 = Standardisation of KMnO4 KMnO4 x Oxalic acid Trial Volume of oxalic no. acid (V1)

Burette readings Initial Final

Volume of KMnO4 (V2)

Normality of KMnO4, N2 = (V1 X N1)/V2 = = Volume of oxalic acid Volume of water Initial concentration Volume of KMnO4 (V1) Volume of filtrate(V2) Charcoal added

Department of Chemistry
Eqilibrium conc. of acid; Ce Oxalic acid adsorbent(x) x/m Log x/m Log Ce Ce /(x/m)

I. From log Ce Vs log x/m graph log x/m = therefore,x/m = But m = 2 Co = x x 1000 VxE = + Ce therefore, x =

From langmuir adsorption isotherm Ce/(x/m) = Ce /b Intercept, 1/ab Slope m, = dy/dx a b 1/a = = = + 1/ab = =1/b = Y = mx + c

Result: From langmuir adsorption isotherm concentration of given Oxalic acid = a= b= From log Ce vs log x/m graph, concentration of given Oxalic acid =

Department of Chemistry

PHASE DIAGRAMS
Two component system of solids
Introduction The most common method employed to obtain the freezing point diagram of binary mixture is thermal analysis method. The method consists in the cooling of a molten mixture of the components and a cooling curve is drawn between temperature and time. The cooling curve ia a continuous one as long as there is no phase change during cooling. When a solid starts seperating the rate of cooling is decreased due to the liberation of heat. Consequently the cooling curve exhibits a break at the freezing point. Suppose a liquid mixture of two components X and Y is cooled slowly. At first its temperature would fall regularly along the curve AB, until the freezing point of the solution is reached at which the liquid become saturated with X. with crystallisation of X there would be a reduced rate of fall of temperature owing to evolution of latent heat, but since the solution would be constantly flowing more concentrated in Y, the freezing point would fall along CD. In practice the transition from AB to CD is rarely ideal, more often a solution super cooled below its true freezing point B to some temperature B and when crystallisation of X commences there is a sudden evolution of heat which temporarily sends the temperature up to C .Eventually the solution reaches saturation w.r.t Y as well as X.Then solid X and solid Y crystallise outside by side in the same proportions as they are present in the solution the temperature remains constant the eutectic point. _______________________________________________________________________

Experiment 1:
Aim:

Phase Diagram of Napthalene Biphenyl System

_______________________________________________________________________ To determine the eutectic temperature of a two component system and also determine the unknown composition Theory: In order to obtain a phase diagram a number of mixtures of A and B having different composition are prepared. Each mixture is heated to a liquid and the cooling curve is obtained for each mixture. From the cooling curve the maximum temperature of first arrest for each mixture and also the temperature of complete halt

Department of Chemistry
(eutectic temperature) are determined. The freezing points are plotted against the composition. The freezing points are plotted against the temperature. From the liquids curve ACB obtained the composition of the given mixture of A and B can be determined. Requirements: Flat bottomed test tubes, Napthalene, Biphenyl. Procedure: Prepare the following mixtures of the components by taking weighed amounts in properly labeled flat bottomed test tubes. Napthalene % Biphenyl % 100 00 90 10 70 30 50 50 30 70 10 90 00 100 sensitive thermometer, air jacket, water bath,

Using a cork fit up a sensitive thermometer and a ring stirrer in the test tube. Melt the contents in a water bath, wipe it clean and place it in an air jacket. Allow the temperature to fall , stir thoroughly and record the temperature every half minute continue to record temperature until it remain constant and the whole mass solidifies. Similarly repeat the determination with other mixtures. Draw the cooling curve for each of the mixture and from each of the mixture determine the maximum temperature of first arrest. Plot the value of freezing point against the percentage composition. From the phase diagram eutectic temperature and eutectic compositions are found out. Composition of unknown mixture: The cooling curve of the unknown mixture is constructed. A line is drawn corresponding to its freezing point in the phase diagram. The line cuts the diagram at two points. Now one of the components is added to mixture and again the freezing point is determined. The shift in the freezing point is found out and the correct point, out of the two is selected and the unknown composition is found out. Observation: Composition Biphenyl % Napthalene % Time I II I 00 100 II 10 90 III 30 70 IV 50 50 V 70 30 VI 90 10 VII 100 00

Temperature of Compositions III IV V VI VII

Result:

10

Department of Chemistry
________________________________________________________________________

Experiment 2: Critical Solution Temperature: Phenol Water system _________________________________________________________________

Aim: To determine the critical solution temperature of phenol water system. Theory:

In general liquids become more soluble with increasing temperature and eventually a temperature will be reached when the liquids become completely miscible. This temperature is known as critical solution temperature or consolute point. The solubility of phenol in water increases on increasing temperature. At a particular temperature (upper consolute temperature) the two liquids are miscible in each other and the solution becomes homogeneous. Requirements: Flat bottomed test tubes, sensitive thermometer, air jacket, water bath, Phenol, Water. Procedure: 5ml of phenol is measured out into a flat bottomed test tube in which a thermometer is also inserted. 3ml of water is added and placed in a water bath and stirred continuously. At a certain temperature the turbidity disappears and at a slightly lower temperature turbidity reappears. The average of the two temperatures is found out and taken as miscibility temperature at that composition. Now 1ml water is added and the corresponding temperatures of complete miscibility are found out. This is repeated by adding 1ml each. A graph is plotted with temperature on Y-axis against composition (% by weight) of phenol on X-axis. The maxima of parabolic curve give CST of Phenol water system. Observation: Volume of water (ml) Temperature of Turbidity Disappearance Appearance Miscibility Temperature % Composition of phenol

Result:

11

Department of Chemistry
__________________________________________________________________

Experiment 3: Effect of Electrolytes on CST KCl Phenol system

Aim:

___________________________________________________________________ To determine the effect of impurity on CST and to find the concentration of unknown KCl solution Theory: Impurities have a regular effect on the CST of Phenol-water system. When KCl solutions of different concentrations are used. The CST is found to increase with concentration of KCl solution (electrolyte). A straight line graph can be plotted and from the graph concentration of the given electrolyte can be found. Requirements: Flat bottomed test tubes, sensitive thermometer, air jacket, water bath, Phenol, KCl. Procedure: The CST of Phenol water system is found out using 0.002M KCl (electrolyte) instead of pure distilled water. The same is repeated with 0.04M, 0.06M, 0.08M and 0.1M solution of electrolyte. A graph is plotted with CST against concentration of electrolyte solution. The CST corresponding is found out and from the graph the concentration of KCl is determined. Observation: Volume of phenol = Volume of KCl (ml) 0.02M KCl Temperature of Turbidity Disappearance Appearance Miscibility Temperature % Composition of phenol

0.04M KCl 0.06M KCl 0.08M KCl 0.1M KCl

Unknown

Result:

12

Department of Chemistry
___________________________________________________________________

Experiment 4: Effect of Electrolytes on CST Succinic acid Phenol system

Aim:

___________________________________________________________________ To determine the effect of immpurity on CST to find the concentration of unknown succinic acid solution. Theory: Impurities have a regular effect on the CST of Phenol water system. If succinic acid solutions of different concentration are used, the CST is found to decrease with concentrations of acid solution. A straight line graph can be plotted and from the graph concentration of given acid solution is found out. Procedure: The CST of Phenol water system is found out using 0.5 of succinic acid solution instead of pure distilled water. The same is repeated using 1%, 1.5% upto 4% solution of succinic acid. A graph is plotted with CST against the concentration of succinic acid. The CST corresponding to succinic acid solution of unknown concentration is found out and from the graph concentration of acid is determined. Observation: Volume of phenol = Volume of Acid Temperature of Turbidity Disappearance 0.5% Appearance Miscibility Temperature % Composition of Phenol

1%

1.5%

2%

13

Department of Chemistry

2.5%

3%

3.5%

4%

4.5%

5%

Result:

14

Department of Chemistry
__________________________________________________________________

Experiment 5: Three Component systems - Determination of Unknown Concentration Water Toluene -Acetic acid system
___________________________________________________________________ Aim: To construct a phase diagram of CH3COOH C6H5-CH3 and H2O. Also to determine concentration of unknown mixture. Theory: The mutual solubility of a pair of partially miscible liquids may be markedly altered by the addition of a third component. In general when the third component is soluble is in only one of the other two components; the mutual solubility of the two liquids is decreased. Then the third component is soluble in both the components their mutual solubility is increased. On mixing water and toluene we get two conjugate solutions of different composition. When CH3COOH acid is added to these, the mutual solubility of water and toluene increases and a point is reached at which the mixture become homogenous which depend on the relative composition of water and toluene mixture. Procedure: Toluene and water is taken in different composition such that the total volume is kept constant (say10ml) in different small conical flasks. Acetic acid is added from the burette to each bottle with constant shaking till the turbidity disappears. The percentage composition by weight of each component is represented on the three corners of triangular graph. From the amount of H2O added and the initial amount of toluene and acetic acid, the percentage composition of the mixture when the turbidity appears, is plotted in the triangular diagram. The points obtained are joined by a smooth curve. A definite volume of the mixture of unknown composition consisting of water and acetic acid is taken and its density is found out. Now toluene is added form the burette till turbidity appears. The percentage by weight of toluene is calculated and a line corresponding to this point is drawn parallel to AC (acetic acid-water axis). This cuts the graph at a point. A line is drawn from the opposite apex B to this point. And extrapolated to touch the line AC. This experiment is repeated to get the composition of the given mixture. Obsevations: Sl no: Volume C6H5CH3 CH3COOH Weight C6H5CH3 % CH3COOH Composition C6H5CH3 CH3COOH

H2O

H2O

H2O

15

Department of Chemistry
Weight Weight Weight Weight Weight of of of of of empty bottle bottle + water water toluene acetic acid = = = = = = = = = = = = = = Relative density of toluene volume = = =

Relative density of water Relative density of CH3COOH Relative density of toluene Weight of bottle + unknown Weight of unknown Relative density of unknown Weight of toluene Relative density of toluene Weight of toluene Weight of mixture % Composition of toluene Result:

___________________________________________________________________

Experiment 5.1: Tie-line for H2O-C6H5CH3-CH3COOH system

Aim: To construct the tie line for Water- Toluene- Acetic acid system. Theory:

____________________________________________________________

In this a mixture of three components are prepared. The three layers are then analyzed separately. The composition of each of the layer by a point is then separated and a curve known as bimodal curve is drawn. Any mixture within the area enclosed by the curve and the base of the triangle will itself resolve into two liquid layers and ay mixture outside this area will form one liquid area. Any line connecting only one conjugate solution, which is in equilibrium with one another, is called a tie line. When the composition of two layers becomes identical the tie line shrinks to a point. Procedure: A homogenous mixture of three components having a composition within bimodal curve is prepared. The mixture was shaken thoroughly and allowed to settle to two layers. Separate the layers using a separating funnel. A small amount of each layer is taken out into a previously weighed dried conical flask and titrated using NaOH using phenolphthalein as indicator. A line is drawn connecting these points on the curve and the point corresponds to the system.

16

Department of Chemistry
Observation : Sl.No Liquid Layer Volume Burette Reading Initial Final Volume of NaOH

Weight of Water Weight of Organic layer Weight of Aqueous layer

= = = = Weight of Aqueous layer/ Weight of Water = Weight of Organic layer/ Weight of Water = = = =

Relative density of Aqueous layer Relative density of Organic layer

Normality of Organic layer Weight/liter of CH3COOH in Organic layer Weight of acetic acid in 1ml of Organic layer % By weight of acetic acid in 2ml organic layer

Normality of aqueous layer = Weight/liter of CH3COOH In aqueous layer = Weight of acetic acid in 1ml of aqueous layer = % By weight of CH3COOH in 2ml of aqueous layer = Result:

________________________________________________________________________

Experiment 7: Three Component systems - Determination of Unknown Concentration Water Chloroform Acetic acid system
________________________________________________________________ Aim: To determine the unknown composition of the given mixture. Theory: The mutual solubility of a pair of partially miscible liquids may be markedly altered by the addition of a third component. In general when the third component is soluble is in only one of the other two components; the mutual solubility of the two liquids is decreased. Then the third component is soluble in both the components their mutual solubility is increased. On mixing water and chloroform we get two conjugate solutions of different composition. When CH3COOH acid is added to these, the mutual solubility of water and chloroform increases and a point is reached at which the mixture become homogenous which depend on the relative composition of water and chloroform mixture.

17

Department of Chemistry
Procedure: Chloroform and water is taken in different composition such that the total volume is kept constant (say10ml) in different small conical flasks. Acetic acid is added from the burette to each bottle with constant shaking till the turbidity disappears. The percentage composition by weight of each component is represented on the three corners of triangular graph. From the amount of H2O added and the initial amount of chloroform and acetic acid, the percentage composition of the mixture when the turbidity appears, is plotted in the triangular diagram. The points obtained are joined by a smooth curve. A definite volume of the mixture of unknown composition consisting of water and acetic acid is taken and its density is found out. Now chloroform is added form the burette till turbidity appears. The percentage by weight of chloroform is calculated and a line corresponding to this point is drawn parallel to AC (acetic acid-water axis). This cuts the graph at a point. A line is drawn from the opposite apex B to this point, and extrapolated to touch the line AC. This experiment is repeated to get the composition of the given mixture. Observations: Sl no: Volume H2O CHCl3 Weight H2O CHCl3 % Composition H2O CHCl3 CH3COOH

CH3COOH

CH3COOH

Weight Weight Weight Weight Weight

of of of of of

empty bottle bottle + Water Water Chloroform Acetic acid

= = = = = = = = = =

Relative density of Water Relative density of CH3COOH Relative density of Chloroform Weight of bottle + unknown Weight of unknown

Relative density of unknown = Weight of Chloroform = Relative density of Chloroform = Weight of Chloroform = Relative density of Chloroform volume = Weight of mixture = % Composition of Chloroform = Result:

18

Department of Chemistry

_______________________________________________________________________

Experiment 8: Three Component systems Tie line of Water Chloroform Acetic acid system _________________________________________________________________
Aim: To construct the tie line for water-chloroform- acetic acid system. Theory: In this a mixture of three components are prepared. The three layers are then analyzed separately. The composition of each of the layer by a point is then separated and a curve known as bimodal curve is drawn. Any mixture within the area enclosed by the curve and the base of the triangle will itself resolve into two liquid layers and ay mixture outside this area will form one liquid area. Any line connecting only one conjugate solution, which is in equilibrium with one another, is called a tie line. When the composition of two layers becomes identical the tie line shrinks to a point. Procedure: A homogenous mixture of three components having a composition within bimodal curve is prepared. The mixture was shaken thoroughly and allowed to settle to two layers. Separate the layers using a separating funnel. A small amount of each layer is taken out into a previously weighed dried conical flask and titrated using NaOH using phenolphthalein as indicator. A line is drawn connecting these points on the curve and the point corresponds to the system. Observations: SL no: Liquid layer Volume Burette reading Initial Final Volume of NaOH

Weight of Water Weight of Organic layer Weight of Aqueous layer Relative density of Aqueous layer Relative density of Organic layer

= = = = Weight of Aqueous layer/ Weight of Water = Weight of Organic layer/ Weight of Water = = = = = = =

Normality of Organic layer Weight/liter of CH3COOH in Organic layer Weight of acetic acid in 1ml of Organic layer % By weight of acetic acid in 2ml organic layer Normality of aqueous layer Weight/liter of CH3COOH In aqueous layer Weight of acetic acid in 1ml of aqueous layer

19

Department of Chemistry
% By weight of CH3COOH in 2ml of aqueous layer = Result:

PARTITION COEFFICIENTS
___________________________________________________________________ ___________________________________________________________________ Aim: To determine the partition coefficient of Iodine between CCl4 and Water. Theory: If a solute is shaken up with two immiscible solvents, it will distribute itself between the two solvents in such a way that the ratio of concentration of the solute in two solvents remains constant, provided the solute remain in the same molecular state in both the solvents. If C1 is the concentration of the solute in solvent I and C2 in in solvent II then C1/C2 = k Where, K is called the partition coefficient. Requirements: I2 in CCl4, K2Cr2O7, Na2S2O3.5H2O,10% KI, starch, Distilled H2O, CCl4, Procedure: In three 250ml stoppered conical flask the solutions are mixed in the following order. Reagents Bottle 1 Bottle 2 Bottle 3 I2 in CCl4 10 15 20 CCl4 10 5 0 Water 100 100 100 The contents of the bottles are shaken well for about hr to attain equilibrium. The bottles are kept in constant temperature bath or left alone for hr. When the equilibrium is reached 2ml of CCl 4 layer of each bottle is titrated against N/10 sodium thiosulphate solution after adding 10ml of 10% KI and 25ml water using starch solution as indicator. The addition of water helps in the titration by gradually extracting I2 into water layer, where the reaction with sodium thiosulphate occurs. 20ml of aqueous layer from each bottle is titrated with N/100 sodium thiosulphate 10 times in a standard flask. Observation: Weight of K2Cr2O7 = Standardisation of Na2S2O3.5H2O N/10 Na2S2O3 x K2Cr2O7 (starch) Volume of K2Cr2O7 pipetted Burette reading Initial Final Vol of N/10 Na2S2O3

Experiment 1: Partition Coefficient of Iodine between CCl4 and Water.

20

Department of Chemistry
Normality of K2Cr2O7 Normality of Na2S2O3 Estimation N/10 Na2S2O3 Vs I2 in Organic layer (starch) Bottle No Volume of organic Burette reading layer pipetted Initial Final Vol of N/10 Na2S2O3 = mass/lit Eq. wt =

Estimation N/100 Na2S2O3 Vs I2 in aqueous layer (starch) Bottle No Volume of aq Burette reading Vol of N/10 Na2S2O3 layer pipetted Initial Final

Volume of N/10 Na2S2O3 solution 2ml of CCl4 layer = V1 Volume of N/100 Na2S2O3 solution 20ml of H2O Solution = V2 Volume of N/100 Na2S2O3 solution 20ml of CCl4 layer = V1 X 10 X 10 Partition Coefficient,K = (V1 X 100)/V2 Bottles I II III V1 V2 K

Result: The partition coefficient of Iodine between CCl 4 and water=

__________________________________________________________________

Experiment 2: Study of equilibrium constants KI + I2 KI3

Aim:

___________________________________________________________________ To determine the equlibrium constant of the reaction KI + I2 KI3 by distribution method. Principle:

21

Department of Chemistry
If Iodine is added to an aqueous KI solution the following equlibrium exists. KI + I2 KI3 or I- + I2 I3The equilibrium constant of the reaction is given by K= [ KI3 ] [ KI ] [ I2 ] Since molecular iodine is soluble in both aqueous and organic phase, if I2 s added to a system of CCl 4 and aqueous KI solution of known concentration, it gets distributed between the two phase. In the system consisting of iodine, KI, and CCl4, the total concentration of I2 in aqueous layer is given by the sum of the concentration of the free iodine in aqueous layer and that of KI3 of I3-.The total concentration of Iodine in CCl4 layer can be found by titration with standard Na2S2O3 Knowing the partition coefficient of iodine between CCl 4 and water, the concentration of free iodine (uncombined) in aqueous layer can be calculated. The concentration of KI3 is obtained by subtracting the concentration of free iodine in aqueous layer. Then calculate the difference of initial concentration of KI and concentration of KI3 formed from the concentration of KI that has reacted. This gives the concentration of KI at equilibrium. This reciprocal of equilibrium constant k gives the instability constant of the complex KI3-Instability Constant = [ KI ] [ I2 ] [ KI3 ]

Requirements: I2 in CCl4, K2Cr2O7, Na2S2O3.5H2O,10% KI, starch, Distilled H2O, CCl4, Procedure: Take 3 stoppered bottles and label them. Prepare approximately 0.1N KI solution and in the 3 bottles in the solution are taken as follows. Bottle No I II III KI solution 50ml 50ml 50ml I2/CCl4 20ml 15ml 10ml CCl4 0ml 5ml 10ml

All the above bottles are stoppered and shaken well for half an hour and set aside in a thermostate. 5ml of organic layer is titrated with N/10 Na2S2O3 after adding 10ml 10%KI solution and water using starch as indicator. Similarly 10ml of the aqueous layer is titrated against the same thiosulphate solution directly. Repeat the titration for the organic and the aqueous layer from bottle II and III also. Observation: Weight of K2Cr2O7 = Standardisation of Na2S2O3.5H2O N/10 Na2S2O3 x K2Cr2O7 (starch) Volume of K2Cr2O7 pipetted Burette reading Initial Final Vol of N/10 Na2S2O3

22

Department of Chemistry

Normality of K2Cr2O7 Normality of Na2S2O3 Normality of KI Estimation

= mass/lit Eq. wt = =

N/10 Na2S2O3 Vs I2 in Organic layer (starch) Bottle No Volume of organic Burette reading layer pipetted Initial Final

Vol of N/10 Na2S2O3

Estimation N/10 Na2S2O3 Vs I2 in aqueous layer (starch) Bottle No Volume of aq Burette reading Vol of N/10 Na2S2O3 layer pipetted Initial Final

Calculation: Partition Coefficient = Bottle 1: Concentration of I2 in CCl4, C2 = N/2 = Concentration of I2 in aq layer,C1 = N/2 = Concentration of I2 ,C4 = C2/D = Combined Iodine = C1 - C2/D = Concentration of KI in equation = Normality of KI Combined Iodine K1 = = [ KI3 ] = C1 [ KI ] [ I2 ] [ KI ] C4 Bottle 2: Concentration of I2 in CCl4, C2 = N/2 = Concentration of I2 in aq layer,C1 = N/2 = Concentration of I2 ,C4 = C2/D = Combined Iodine = C1 - C2/D = Concentration of KI in equation = Normality of KI Combined Iodine K2 = = [ KI3 ] [ KI ] [ I2 ] = C1 [ KI ] C4

23

Department of Chemistry

Bottle 3: Concentration of I2 in CCl4, C2 = N/2 = Concentration of I2 in aq layer,C1 = N/2 = Concentration of I2 ,C4 = C2/D = Combined Iodine = C1 - C2/D = Concentration of KI in equation = Normality of KI Combined Iodine K3 = = [ KI3 ] = C1 [ KI ] [ I2 ] [ KI ] C4 Result:

___________________________________________________________________

Experiment 3: Determination of concentration of KI solution

Aim:

___________________________________________________________________ To determine the concentration of given KI solution from the equilibrium constant of the reaction KI + I2 KI3 Principle: In a separate experiment using standard solution of KI, the equilibrium constant k is determined .Then using the given KI solution. The experiment is repeated using the value of k obtained before and the strength of the given KI solution is calculated. Instability Constant, k, = [ KI ] [ I2 ] [ KI3 ] [ KI ] = k [ KI3 ] [ I2 ] From the experiment the equilibrium constant of KI is obtained. The initial concentration of KI solution is obtained by adding the concentration of KI 3 to the equilibrium constant. Requirements: I2 in CCl4, K2Cr2O7, Na2S2O3.5H2O,10% KI, starch, Distilled H2O, CCl4, Procedure: In a stoppered bottle 50ml of given KI solution,10 ml of I2/CCl4 and 10ml of pure CCl4 are added, shaken for half an hour and is labeled bottle III. Similarly Bottle I and II are prepared as before and shaken, kept in a thermostate along with other bottles containing standard KI. Bottle No I II III KI solution 50ml 50ml 50ml I2/CCl4 20ml 15ml 10ml CCl4 0ml 5ml 10ml

5ml of CCl4 layer is titrated against N/10 Na2S2O3 and 10ml of aqueous layer against N/10 Na2S2O3 solution.

24

Department of Chemistry
From the title value, instability constant and hence the concentration of given KI is obtained. Observation: Weight of K2Cr2O7 = Standardisation of Na2S2O3.5H2O N/10 Na2S2O3 x K2Cr2O7 (starch) Volume of K2Cr2O7 pipetted Burette reading Initial Final Vol of N/10 Na2S2O3

Normality of K2Cr2O7 Normality of Na2S2O3 Estimation

= mass/lit = Eq. wt =

N/10 Na2S2O3 Vs I2 in Organic layer (starch) Bottle No Volume of organic Burette reading layer pipetted Initial Final

Vol of N/10 Na2S2O3

Estimation N/10 Na2S2O3 Vs I2 in aqueous layer (starch) Bottle No Volume of aq Burette reading Vol of N/10 Na2S2O3 layer pipetted Initial Final

Calculation: Bottle 1: Concentration of I2 in CCl4, C2 = N/2 = Concentration of I2 in aq layer,C1 = N/2 = Concentration of I2 ,C4 = C2/D = Combined Iodine = C1 - C2/D = Concentration of KI in equation = Normality of KI Combined Iodine K1 = [ KI3 ] [ KI ] [ I2 ] = C1 [ KI ]

25

Department of Chemistry
[ KI ] = K1 C1 C4 Bottle 2: Concentration of I2 in CCl4, C2 = N/2 = Concentration of I2 in aq layer,C1 = N/2 = Concentration of I2 ,C4 = C2/D = Combined Iodine = C1 - C2/D = Concentration of KI in equation = Normality of KI Combined Iodine K2 = [ KI3 ] [ KI ] [ I2 ] [ KI ] = K2 C1 C4 = C1 [ KI ]

Bottle 1:

Concentration of I2 in CCl4, C2 = N/2 = Concentration of I2 in aq layer,C1 = N/2 = Concentration of I2 ,C4 = C2/D = Combined Iodine = C1 - C2/D = Concentration of KI in equation = Normality of KI Combined Iodine K3 = [ KI3 ] [ KI ] [ I2 ] [ KI ] = K3 C1 C4 Result: = C1 [ KI ]

________________________________________________________________________

Experiment 4: Partition-Coefficient of Benzoic acid between C6H6 and H2O

Aim:

________________________________________________________________________ To find the partition coefficient of benzoic acid between benzene and water and to find the the association of benzoic acid in benzene. Principle: When benzoic acid is distributed between benzene and water Corg/Caq is not found to be a constant. But the value (Corg)/Caq is found to be constant showing that benzoic acid exist as dimer in benzene. Procedure: Weigh out 1,2,3g of benzoic acid and transfer them to different stoppered bottles, Add 50ml water and 50ml benzene to each bottle shake for 1 hour. Titrate 5ml benzene layer and 10ml aqueous layer with N/10 and N/100 NaOH solution

26

Department of Chemistry
using phenolphthalein indicator. The partition Coefficient of benzoic acid between water and benzene are determined.

Contents Benzoic acid Water Benzene Observation:

Bottle I 1g 50ml 50ml

Bottle II 2g 50ml 50ml

Bottle III 3g 50ml 50ml

Normality of NaOH used for titration of benzene layer,N1 = N/10 Normality of NaOH used for titration of aqueous layer,N1 = N/100 Estimation Benzoic acid in Benzene layer Vs N/10 NaOH (phenolphthalein) Bottle No Volume of benzene Burette reading Vol of N/10 NaOH layer pipetted, V2 N1 Initial Final

Concentration of Benzoic acid Corg = (V1 x N1)/V2 = Estimation Benzoic acid in Aqueous layer Vs N/100 NaOH (phenolphthalein) Bottle No Volume of Aqueous Burette reading Vol of N/100 NaOH layer pipetted, V2 N1 Initial Final

Concentration of Benzoic acid Caq = (V1 x N1)/V2 = Partition Coefficient, K1 = (Corg)/Caq = K2 = (Corg)/Caq = K3 = (Corg)/Caq = Result: Partition Coefficients = K = (Corg)/Caq is found to be a constant. It shows that benzoic acid has undergone dimerisation in benzene.

27

Department of Chemistry

VISCOMETRY
________________________________________________________________________

Experiment 1: Verification of J-Kendalls equations

Aim:

________________________________________________________________________ To verify Kendalls equation from viscosity measurements Principle: Kendalls equation is Log AB = xA log A + xB log B Where, AB XA XB A B = fluidity of mixture = mole fraction of compound A = mole fraction of compound B = fluidity of compound A = fluidity of compound B therefore xB =1-xB

but xA + xB =1 ; log AB

= xA(log A-log B )+ log B

Now AB is plotted against mole fraction x .The slope of the graph gives the value of (log A log B). The value of the slope is compared with that of calculated value. Procedure: The Viscometer is cleaned and a constant volume of the mixture is introduced into it and its time of flow is determined separately. Then a number of mixtures are prepared and their times of flow are determined. Mole fraction of a particular component is plotted against the fluidity of the mixture. Then from the graph, slope is found and compared with the theoretical value. Observations: Liquid composition Fluidity =1/ Weight of Log

28

Department of Chemistry

Weight of

Number of moles of A

Number of moles of B

Total

Mole fraction xA = nA / (nA+ nB)

Calculations: A = 1/A log A log B slope from calculations, log A - log B slope from the graph, dy/dx Result: ________________________________________________________________________ = = = = =

Experiment 2: Composition Determination

Aim:

________________________________________________________________________

To determine the composition of the given mixture of two liquids. Principle : The coefficient of viscosity of given liquid can be called as , 1 / 2 = d1t1/d2t2

29

Department of Chemistry
Where, d1 and d2 are the density of the liquids ; t1 and t2 are the time of flow of the liquids. The coefficients of viscosity and composition of solution, we get a straight line from which the composition of unknown mixture can be determined. Procedure: Ostwalds viscometer is cleaned and dried. It is fitted vertically on a stand .A mixture of different compositions are prepared by mixing the two liquids of different proposition. Time of flow for each of these is determined. Each time same amount of liquid is taken. The time of flow for the given unknown are also determined. A graph is plotted between viscosity and composition of solution and with the help of it composition of given unknown mixture is obtained. Observations: Liquid composition Flow time 2 Mean Relative density Coefficient of viscosity Percentage composition of

Unknown

Calculations: Relative density, 1 = = Mass of empty bottle Mass of bottle and unknown Mass of unknown Relative density of unknown = = = = weight of unknown Weight of water v1d1+v2d2

Coefficient of viscosity of unknown = Result: Percentage composition of unknown mixture % of = % of =

30

Department of Chemistry

__________________________________________________________ Experiment 1: Determination of Molecular Weight

________________________________________________________________________ Aim: To determine the molecular weight of an unknown solute using naphthaline as the solvent. Principle: When a non volatile solute is added the freezing point of the solvent is lowered. The difference in the freezing point of the pure solvent and the solution is referred to as the depression in freezing point. And it is related to the molecular weight of the nonvolatile solute as given below. M = (kf X w X 1000)/ T X W Where w is the weight of the solute of molecular mass M and W is the weight of the solid solvent. Knowing the depression in freezing point (T) and the cryoscopic constant (kf ) of naphthalene, the molecular weight of unknown solute can be calculated. Advantage of the solid cryoscopy over liquid cryoscopy is that in solid cryoscopy ordinary thermometer are used and the measurements are too easy. Requirements: Flat bottom test tube, Naphthalene, Biphenyl, water bath Procedure: A clean dry flat bottomed test tube is weighed and about 2/3 of it is filled with naphthalene and again weighed. Then it is closed with a two holed cork through which a stirrer and a sensitive thermometer are introduced. Naphthalene in the tube is melted by dipping the tube in a boiling water bath. When the naphthalene melts, it is removed from water bath and then the tube is placed in an air jacket with constant stirring. The time-temperature observation is done for every half a minute. At first the temperature slowly decreases and then remains at a particular temperature for some times. This corresponds to the freezing point. Some times the temperature may fell below this temperature first and then rise and remain constant for some time. About 0.2gm of the unknown solute is then accurately weighed and added to the solvent mixture is melted and mixed well. It is then placed in an air jacket and determines the freezing point as before. The experiment is repeated by a second addition of unknown solute to the same system and graph is plotted.

31

Department of Chemistry
Observation: Time Solvent 1st Addition 2nd Addition 3rd Addition

Result: The Molecular weight of given solute =

__________________________________________________________ Experiment 2: Determination of Cryoscopic Constant

________________________________________________________________________ Aim: To determine the molecular weight of an unknown solute using naphthaline as the solvent. Principle: When a non volatile solute is added the freezing point of the solvent is lowered. The difference in the freezing point of the pure solvent and the solution is referred to as the depression in freezing point. And it is related to the molecular weight of the nonvolatile solute as given below. Kf = (M X W X T) / 1000 X w Where w is the weight of the solute of molecular mass M and W is the weight of the solid solvent. Knowing the depression in freezing point and the molecular weight of solute, the Cryoscopic constant of unknown solvent can be calculated. Advantage of the solid cryoscopy over liquid cryoscopy is that in solid cryoscopy ordinary thermometer are used and the measurements are too easy. Requirements: Flat bottom test tube, Naphthalene, Biphenyl, water bath Procedure: A clean dry flat bottomed test tube is weighed and about 2/3 of it is filled with naphthalene and again weighed. Then it is closed with a two holed cork through which a stirrer and a sensitive thermometer are introduced. Naphthalene in the tube is melted by dipping the tube in a boiling water bath. When the naphthalene melts, it is removed from water bath and then the tube is placed in an air jacket with constant stirring. The time-temperature observation is done for every half a minute. At first the temperature slowly decreases and then remains at a particular temperature for some times. This corresponds to the freezing point. Some times the temperature may fell below this temperature first and then rise and remain constant for some time. About 0.2gm of the unknown solute is then accurately weighed and added to the solvent mixture is melted and mixed well. It is then placed in an air jacket and determines the freezing point as before. The experiment is repeated by a second addition of unknown solute to the same system and graph is plotted. Observation:

32

Department of Chemistry
Time Solvent 1st Addition 2nd Addition 3rd Addition

Result: The Molecular weight of given solute = ___________________________________________________________________

HEAT OF SOLUTION BY SOLUBILITY DETERMINATION

Aim:

___________________________________________________________________ To determine the heat of a solution of a given substances by solubility method. Principle: The dissolution of a solid into a liquid is usually accompanied with a heat effect, heat absorbed or evolved. The heat absorbed or evolved where 1 mole of the solid is dissolved into a solution, which is already practically saturated differ from that of infinite dilution from saturation to infinite dilution. The influence of temperature on solubility is best expressed by Vant hoff equation ie. D ln S/dt = H/RT2 Where, S is the solubility of the salt in moles per 1000g of the solvant and H is the heat of a solution per mole. On integration of the above expression, we have log S = - H +C 2.303 RT H is assumed to be independent of temperature; A plot of log S values (ordinate) against corresponding value 1/T (abscissa) will practically be a straight line or a smooth curve. The slope of the straight line is H/2.303R. Thus H can be calculated. Alternatively, integrating equation between 2 temperatures T1 and T2 we get logS2 logS1 = H |1- 1| 2.303 | T2 T1| It is thus seen that of two solubility temperatures are determined. The mean of heat of solution between the two temperature limits can be calculated. Procedure: 1. Place about 60-70 cc of distilled water in a small beaker suspended in a large beaker containing water at a temperature about 13-15oC above the room temperature. Add increasing amount of benzoic acid to the beaker with efficient stirring until a small amount of solid remain undissolved. 2. Allow the solution to cool and when the temperature reaches about 10C above the room temperature, record the temperature to 1C and immediately withdraw 10cc of the saturated solution using a pipette. To prevent sucking of small crystals into the pipette along with the solution, small piece of filter paper is tied at the tip of the pipette. The pipette is previously warmed by passing through the flame of the

33

Department of Chemistry
Bunsen burner before pipetting in the solution. So as to prevent the separation of the solid in the pipette at low temperature. 3. Remove the piece of filter paper from the tip of pipette and draw the pipette into a weighing tube. Reweigh the weighing tube. 4. Carefully transfer the solution together with the washings into a conical flask and titrate it with 0.5M NaOH solution using phenolphthalein as the indicator. In this way determine the weight od acid dissolved in the known weight of the solution and hence in a known weight of the solvent. 5. Make duplicate determination at the same temperature. Allow the solution to cool down further to room temperature. Make duplicate determination at room temperature.

Volume of Acid

Temperature of Turbidity Disappearence Appearance

Miscibility Temperature

% Composition of Phenol

0.5% 1% 1.5% 2% 2.5% 3% 3.5% 4% 4.5% 5%

34