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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES

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Solution A solution is a homogenous mixture of two or more substances whose composition may be different within certain limits. Though the solution is homogenous in nature but it retains the properties of it's constituents. The substances, making up the solutions are called components of the solution. If NaCl is dissolved in water, then NaCl and H2O are the components of solution. If two components are there in the solution it is called binary solution. Similarly for three components it is called tertiary solution and for four components we say quaternary solution. The two components of binary solution are called Solute and Solvent. Solvent is that component in the solution whose physical state is the same as that of the resulting solution while the other component is called Solute. eg. Suppose sugar is dissolved in water and solution is in liquid state, then solution and water are in the same physical state (liquid state), then water is solvent and sugar is solute. For the solutions in which both the components have same physical state as that of solution, then the component which is in less amount is called solute and other is called solvent. In solutions, the components are of molecular size (about 1000 pm) and the components cannot be separated by any of the physical methods such as filtration, settling, centrifugation etc.

Types of solution
Depending upon the physical state of the solvent and solute, solution can be classified into nine types.

Types of solutions
Solvent Gas Gas Gas Liquid Liquid Liquid Solid solid Solid Solute Gas Liquid Solid Gas Liquid Solid Gas Liquid Solid Example Mixture of gas, air Water vapour in air Sublimation of a solid into gas CO2 gas dissolved in water Mixture of miscible liquids Salt in water Absorption of gases over metal, H2 gas over palladium Mercury in copper, mercury in gold Alloys, coloured stones, gems etc.

Among these solution, the most significant type of solutions are those which are in liquid phase. They are: 1. Solid in liquid solution 2. Liquid in liquid solution 3. Gas in liquid solution The solution in which water is the solvent are called aqueous solution and solution in which water is not the solvent are called non aqueous solution The common non-aqueous solvents are ether, Benzene, Carbon Tetrachloride. 1. Solid in liquid solution Here solid is solute and liquid is solvent. The amount of solute dissolved in 100gm of solvent to make a saturated solution at a particular temperature is called Solubility. Solubility depends upon (i) Temperature (ii) Nature of solute and solvent

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES

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Cause of solubility We know that like dissolve like, meaning of this is polar solvents dissolve polar solutes and non polar solvents dissolve non polar solutes. For example ionic compounds like NaCl, KCl etc. are very soluble in water but insoluble in solvents like CCl4 , CS2. Non Polar compds. I2 , S8 are soluble in CCl4 but insoluble in water. The solubility of ionic solution depends upon ion dipole interactions. Due to ion-dipole interaction solvation energy (Hydration energy if water is solvent) is released which is responsible for the dissolution of solute in the solvent. 2. Liquid in liquid solutions When two liquids are mixed which may be completely miscible, partially miscible or immiscible. Causes of miscibility of liquids Chemically alike liquids mix with in one another as compared to others. Alkanes are miscible in all proportions with one another because they are non-polar. If there is dipole-dipole interaction, then two liquids are miscible. Molecular size of liquids which are naturally soluble, are also same. 3. Gas in liquid solution Most of the gases are soluble in water and their solubility depends upon the nature of the gas, temperature and pressure. Oxygen gas is sufficiently soluble in water to permit the survival of aquatic life in oceans, rivers and lakes.

Methods of expressing the concentration of a solution
The concentration of solution may be expressed in many ways. They are as under. o Mass percentage It is defined as the amount of solute present in 100gm of solution. Suppose sugar is dissolved in water and concentration of sugar is 15% by mass. It means 15 gm of sugar is dissolved in 100gm of solution, Similarly, suppose WA gram is the mass of the solute A dissolved in WB gram of solvent B, then total mass of solution = WA +WB gm and Mass Percentage of A = WA / ( WA + WB ) X 100 Volume percentage It is defined as the volume of solute present in 100 volume of solution. Suppose VA is the volume of solute A dissolved in solvent B having Volume VB Then, total volume solution = VA + VB Therefore Volume percentage of A = VA / ( VA + VB ) X 100 Molarity It is defined as the number of moles of solute dissolved in one litre of solution It is represented by M. Therefore Molarity = number of moles of solute / volume of solution (in 1 litre) = w /m X V ( litres) =wX1000/mXV(ml.) If we want to prepare 1 molar solution of NaOH, then we should take one mole NaOH (40gm) and dissolve it in water and make the solution one litre in volume. Molarity is expressed in moles/litre. Molarity of solution can be changed due to increase in temperature because by

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES

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increasing the temperature volume of solution will increase but number of moles in solution will be same. o Normality It is defined as the number of grams equivalent of solute dissolved in one litre solution. It is expressed by N. Normality (N) = number of grams equivalent of solute / volume of solution in litre or, = w / E X V ( litres) =w X 1000 / E X V(ml.) Normality of solution can be changed due to increase in temperature because by increasing the temperature volume of solution will increase but number of gm. Equivalents in solution will be same. A solution having normality one is called normal solution N / 10 solution is called deci normal solution N / 2 solution is called semi normal solution o Molality It is defined as the number of moles of solute dissolved in one kg of solvent. It is represented by m. Molality (m) = number of moles of solute / mass of solvent in kg = w / E X W ( K.g) =w X 1000 / E X W(gm.) It is expressed in units of moles kg-1. The molality of solution does not change with temperature. o Mole fraction Suppose A and B two components have been mixed to make a solution, then mole fraction of A will be equal to the ratio of Number of moles of A to the total number of moles of A and B. Mole fraction is denoted by X (Shi). Here, XA =no. of moles of A / (no. of moles of A + no. of moles of B) And XB =no. of moles of B / (no. of moles of A + no. of moles of B) And XA + XB = 1 In a binary solution, if we know the mole fraction of one component, the mole fraction of other can be calculated. o Formality It is defined as the number of grams formula mass of ionic solute dissolved in one litre of solution. It is represented by F. Formality (F) = no. of gram formula mass of ionic solute / volume of solution in litre A solution containing one gram formula mass of ionic solute in one litre solution is called one formal solution or formal solution. o Parts Per Million (PPM) When a solute present in a very small amount in solution, then concentration is expressed in PPM. It is defined as the number of parts by mass of solute per million parts by mass of the solution. We know O2 is dissolved in sea water. Suppose, a litre of sea water (litre of sea water = 1030 gm)

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
contains 6 x 10-3 gm of dissolved oxygen. Since, 1030 gm of sea water contains 6 x 10-3 gm O2 Therefore 1 gm of sea water contain 6 x 10-3 / 1030 gm O2 Therefore 106 gm of sea water contain = 6 x 10-3 / 1030 x 106 gm O2 = 5.8 gm O2 per 106 gm sea water. Where 5.8 gm O2 is dissolved in 106 gm sea water or one million grams of sea water. Therefore 5.8 PPM is the concentration of O2 in seawater. Atmospheric pollution in cities due to harmful gases is generally given in PPM though in this case the values refer to volumes rather than masses. eg. Suppose it is found that SO2 in the air is 10 PPM. It means that 10cc of SO2 is present in 106 cc or 1000 litre of air.

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Some numerical problems
Q No. 1 Calculate the concentration of solution which is obtained by mixing 200 gm of 25 % solution of NH4 NO3 with 150 gm of a 40% solution of NH4 NO3 (ammonium nitrate). Solu. Total mass of sol. = 200 +150 = 350 gm Amount of NH4 NO3 in 200 gm 25 % sol. = 200 x 25 / 100 = 50 gm. Amount of NH4 NO3 in 150 gm of 40 % sol. = 150 x 40 / 100 = 60 gm. Therefore, total mass of solute = 50 + 60 = 110 gm Therefore, Conc. of sol. = mass of the solute / mass of the sol. x 100 = 100 x 110 / 350 = 31.4 % Q No. 2 HNO3 contain 69 % by mass. Calculate the volume of this solution which contain 19.9 gm of NHO3. (Density of solution = 1.41 gm/cc) Solu. 69 gm HNO3 is present in 100 gm sol. Therefore, 19.9 gm HNO3 is present in 100 / 69 x 19.9 gm solution = 28.8 gm. We will determine volume of solu. whose mass is 28.8 gm and density is 1.41 gm/cc We know D = M / V Therefore V = M / D = 28.8 / 1.41 cc = 20.4 cc Ans. Q No. 3 The concentration H2SO4 in a bottle labelled as 49 % H2SO4 by mass and its density is 1.5 gm/c. Calculate (i) Molarity (ii) Normality (iii) Molality of H2SO4 Sol. 49 % H2SO4 by mass means 49 gm H2SO4 in 100 gm solution (i) Calculation of molarity Molecular mass of H2SO4 = 98 Volume of 100 gm of H2SO4 = Mass / Density = 100 / 1.5 = 66.6 cc here, 49 gm H2SO4 is dissolved in 66.6 cc of solution therefore, Molarity = No. of moles of H2SO4 / Volume of solu. In litre = (49/98) / (66.6/1000) = 49 / 98 x 1000 / 66.6 = 7.5 M (ii) Calculation of normality

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
here, equivalent weight of H2SO4 = Molecular Mass / Basicity = 98 / 2 = 49 Therefore Normality of solution = No. of equivalent weight of H2SO4 / Volume of solution in water = (49/49) / (66.6/1000) = 49 / 49 x 1000 / 66.6 = 15 N. (iii) Calculation of molality of H2SO4 solu. Here mass of H2SO4 in 100 gm solutions = 49 gm Therefore number of moles of H2SO4 = 49 / 98 = 0.5 Mass of water in the solution = 100 - 49 gm = 51 gm therefore, Molality of H2SO4 sol. = Number of moles of H2SO4 / Mass of solvent in kg. = 0.5 / (51/1000) = 0.5 x 1000 / 51 m = 9.8 m or 9.8 mol kg-1 Vapour pressure of solution If a pure liquid is covered with a bell-jar, a part of liquid evaporates and fills the available space with the vapour. The vapours formed will have a tendency to change back to the liquid state by the process of condensation. At a particular temperature, an equilibrium will be established between liquid and vapour phases. The pressure exerted by the vapour in such situation at a given temperature is called the vapour pressure of the liquid or solvent.

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If a non-volatile solute is added to a solvent to make a solution, the vapour pressure of the solution will be the vapour pressure of the solvent because only solvent molecules will be converted in vapour phase. As shown in fig.b. on the surface of the solution, solvent and solute molecules are there. Only solvent molecules will go in to vapour phase because solute is non volatile. On the surface of a solution, now small no. of molecules of solvent are there, less vaporization will take place and so vapour pressure of solution is found to be less than that of pure solvent.

Vapour pressure of a liquid depends upon. 1. Nature of liquid 2. Temperature, vapour pressure increases with increase of temperature 3. Presence of impurities or solute - the presence of non-volatile impurities lower the vapour pressure and presence or addition of volatile impurities (solute) raises the vapour pressure of solutions.

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
Raoult's law
He stated that The vapour pressure of a solution containing non volatile is directly proportional to the mole fraction of solvent Vapour pressure of solution α mole fraction of solvent PA α XA PA = PoA XA PoA is the pressure of pure component A. In a solution of two miscible volatile liquids A and B having mole fraction XA and XB respectively and if their partial vapour pressure is PA and PB then PA α XA PA = PoA XA, PoA is the vapour pressure of pure component A. And PB α XB = PoB XB , PoB is the vapour pressure of pure component B. Now total vapour pressure P, exerted by the solution is the sum of partial pressure PA and PB as per the Dalton's law of partial pressure We may write P = PA + PB The relationship between vapour pressure of a component and its mole fraction is called Raoult's law which states that for a volatile liquid the partial vapour pressure of each component in the solution is directly proportional to its mole fraction. The law will not be applicable if the mixture of volatile liquids do not form a solution. According to Raoult's law for two miscible volatile liquids PA = PoA XA --------- (I) PB = PoB XB --------- (ii) We will take equation (I) here PA = PoA XA When XA = 1, then PA = PoA If we plot a graph between PA and XA we will get a straight line. The maximum value of XA is one, So maximum value of PA will be equal to PoA (Vapour pressure of pure solvent) When XA = 0, then PA = 0 Similarly we can plot a graph between PB and XB and values of PB and XB will change in the same way as above. We get a graph like this

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
Partial and total vapour pressure curves for solutions, which follow Raoult's law. A graph between PA and XA is shown by I in the above figure and its a straight line. A graph between PB and XB is shown by II in the above fig. and it's a straight line. In line III, the total vapour pressure P of solution for any composition is shown. Here, P = PA + PB. The solutions which obey Raoult's law are called ideal solutions. For such solutions, the vapour pressure of the solution always lies between the vapour pressure of the pure components.

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Relative lowering of vapour pressure
Suppose we are considering a solution which is obtained by addition of non volatile solute to the volatile solvent. eg. Glucose dissolved in water. In such type of solution, vapour pressure of solution depends upon the vapour pressure of solvent. Although solute is there but it has no contribution for the vapour pressure. Solute is present on the surface also, so vaporization of solution will be slow and vapour pressure of solution will be less than the vapour pressure of pure solvent. Suppose vapour pressure of solvent is PA Then, PA α XA PA = PoXA ----- (I) XA is mole fraction of solvent, PoA is vapour pressure of pure solvent. Suppose mole fraction of solute is XB Then, we know that XA + XB = 1 Therefore XA = 1 - XB Putting the value of XA in (I) we have PA = PoA (1-XB) = PoA - PoA x XB PoA XB = PoA - PA XB = PoA - PA / PoA Or PoA - PA / PoA = XB ------ (ii) Here, PoA - PA is lowering of vapour pressure and PoA - PA / PoA is called Relative Lowering of Vapour Pressure Equation (ii) is the alternate statement of Raoult's law for solution of non-volatile solutes. Raoult's law for solution of non-volatile solutes The relative lowering of vapour pressure for a solution is equal to the mole fraction of solute when solvent alone is volatile. PoA - PA / PoA = XB If we want to know the behaviour of solutions, Raoult's law is helpful to give the information accordingly.

Colligative properties
The properties of solutions, which depend on the number of solute and solvent particles(molecules or ions) but not upon their nature of the solute are called colligative properties. Here we will take non-volatile solute. Some of the colligative properties are i. ii. iii. iv. Relative lowering of vapour pressure Elevation of boiling point Depression of freezing point Osmotic pressure

Relative lowering of vapour pressure We have already discussed that when a non-volatile solute is added to a solvent, the vapour pressure of solution decreases. Let XA is the mole fraction of solvent, XB is the mole fraction of solute and PoA is the vapour pressure of pure solvent and PA is the vapour pressure of pure solution. Then we have already proved that

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
PoA - PA / PoA = XB Or relative lowering of vapour pressure of an ideal solution containing non volatile solute is equal to the mole function of solute and solvent, when solvent alone is volatile.

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Elevation of boiling point
We know that when the temperature of liquid is raised, its vapour pressure increases. When the vapour pressure of liquids equals to the atmospheric pressure then liquid begins to boil. So boiling point of a liquid may be defined as the temperature at which its vapour pressure becomes equal to atmospheric pressure.

A variation of vapour pressure of solvent and solution at different temperature is shown in the above fig. The curve AB gives the vapour pressure of pure solvent at different temperature and curve C D gives the vapour pressure of solution at different temperature. The curve CD representing the vapour pressure of solution at different temperature lies below the curve AB which corresponds to the vapour pressure of pure solvent. This is only due to fact that vapour pressure of solution is less than that of pure solvent. It is clear from the fig. that the vapour pressure of pure solvent is equal to atmospheric pressure at X and the vapour pressure of solution becomes equal to atmospheric pressure at Y. At X, temperature is Tob and at y it is Tb. It is now clear that Tob is the boiling point of solvent and Tb is the boiling point of solution. Since, Tb is greater than Tob, there is an elevation or increase in boiling point of the solution as compared to that of the solvent. Suppose elevation in boiling point is Δ Tb Therefore Δ Tb = Tb - T ob It is found that the elevation of boiling point is directly proportional to the number of moles of solute in a given amount of solvent. Δ Tb α m or Δ Tb = Kb m where m is molality and kb is called boiling point elevation constant or molal elevation constant or ebullioscopic constant. Here if m = 1 Δ Tb = kb Thus molal elevation constant kb is defined as the elevation in boiling point for 1 molal solution i.e a solution containing 1 gm mole of solute dissolved in one kg of the solvent. Unit of kb is k kg mol-1

Depression of freezing point
The freezing point is the temperature at which the solid and liquid state of substance have the same vapour pressure. It has been observed that when a non-volatile solute is added in a solvent, the freezing point of

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
solution is lower down than the pure solvent. eg. the freezing point of water is Ooc but when a non volatile solute is added to it then freezing point may be -1oC or -1.5oC depending upon the amount of solute. At the freezing point of a solvent, the solid and the liquid are in equilibrium. It means that they must have the same vapour pressure. In pure solvent we are adding some non-volatile solute and making the solution. We also know that vapour pressure of solution in lower than the pure solvent. When a solution freezes, the solid that separates out is the pure solid solvent. Since the vapour pressure of a solution is lower than the pure liquid solvent, then it is natural that a solution and the solid solvent can be in equilibrium only if the vapour pressure of solid solvent can become lower. This will happen if the temperature of freezing of solution is lower than the temperature of freezing of the solvent. Thus, a solution and the pure solid solvent can only be in equilibrium at a lower temperature compared to the temperature at which a pure liquid solvent is in equilibrium with the pure solid solvent.

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In the figure, curve BC gives the vapour pressure of the pure solvent. DE is the vapour pressure curve for the solution at different temperature. The curve AB corresponds to the vapour pressure of the solid at different temperature. B is the point where solvent freezes and at point D solution freezes. To is the freezing point of solvent and T1 is the temperature at which solution freezes and Δ Tf is the freezing point depression. The depression of the freezing point is also a colligative property, because the extent of lowering depends only on the number of molecules of solute and not on its nature. It is found that the depression freezing point is directly proportional to the no. of moles of solute in a given amount of solvent Δ Tf α m Or Δ Tf = Kf m Where m is molality and Kf is called Freezing point depression constant or molal depression constant or molal cryoscopic constant Here if m = 1 Then Δ Tf = kf Thus, molal depression constant kf is defined as the depression in freezing point for 1 molal solution i.e. a solution containing 1 gm mole of solute dissolved in one kg of the solvent. Unit of kf is k kg mol-1 Values of kb and kf for some common solvents are given below.

Solvent Water (H2O) Ethylalchohol Benzene Chloroform Carbon

B.P (k) 373.0 351.5 353.3 334.3 350.0

kb (K kg mol-1) 0.52 1.20 2.53 3.63 5.03

FP1 (k) 273.0 155.7 278.6 209.6 250.5

Kf (K kg mol-1) 1.86 1.99 5.12 4.70 31.8

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
tetrachloride Carbon disulphide

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319.4

2.34

164.2

3.83

Osmotic pressure
When a solution is separated from pure solvent by a semi permeable membrane, then it is observed that the solvent flows from the region of pure solvent in to solution. A semi permeable membrane is a membrane which blocks the solute molecule but allows the passage to solvent molecules only. Animal bladder is an example of natural semi permeable membrane. Parchment paper, cellophone and copper ferrocynide are some examples of artificial semi permeable membranes. If two solutions of different concentration are separated by a semi permeable membrane then the solvent flows from solution of lower concentration to solution of higher concentration. The passage of solvent from pure solvent or from solution of lower concentration to solution of higher concentration through a semi permeable membrane is called osmosis.

In the above fig. an inverted thistle funnel having semi permeable membrane and solution of sugar is placed in it. Semi-permeable membrane may be of animal bladder or parchment paper. The thistle funnel is lowered into beaker containing water. The membrane will allows only the molecules of the solvent and not the solute to pass through it. There will be movement of water molecules from pure solvent into the solution. As a result water passes into the thistle funnel and level of solution in the thistle funnel rises gradually. This process is called Osmosis. The passage of solvent through the membrane can be stopped if adequate pressure is applied on the solution side, this pressure is known as osmotic pressure. Reverse osmosis If the pressure applied on the solution is greater than osmotic pressure, then solvent starts passing from solution into the solvent. This is called reverse osmosis. This principal is used for the purification of sea water or hard water. Sea water is placed in contact with pure water through semi permeable membrane. Pressure greater than Osmotic pressure is applied on sea water. This causes the movement of pure water from sea water side to pure water side.

Isotonic solution
The two solutions having equal osmotic pressure are called Isotonic solutions. 0.9 % NaCl solution is isotonic with human blood. In this solution, the blood cell neither swell or shrink. Therefore medicine are mixed with saline water before being injected in to veins. If the NaCl solution is less concentrated, its osmotic pressure will be low and water will move in to the blood cell causing it to swell and finally burst. On the other hand, if the solution is more concentrated its osmotic pressure will be high and the water of blood cell will move out of the cell causing the cell to shrink. Hypertonic and hypotonic solutions A solution having higher osmotic pressure than some other solution is said to be hypertonic with respect to the other solution. A solution having low osmotic pressure relative to some other solution is called Hypotonic.

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
Osmotic pressure is colligative property and it depends upon the molar concentration of solute but does not depend upon its nature. It is related as under:

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π V = nRT π = n/v RT π = CRT
where n is the number of moles of solute R = gas constant T = Temperature V = Volume of solution C = Concentration of solution in moles/litre or it is molarity By measuring osmotic pressure, molecular mass of solute can be determined. The method is widely used to determine the molecular masses of macromolecules such as protein and polymers. Other colligative properties such as elevation in boiling point or depression in freezing point are too small to be measured. On the other hand measurement of osmotic pressure is done at room temperature and it is measurable for a very dilute solution also. This is useful for biological molecules, as they are generally not stable at higher temperature.

Non ideal solutions and abnormal molecular masses
. Ideal solutions Solutions which obey Raoult's law, are called ideal solutions. This is a very simple definition. According to Raoult's law the partial vapour pressure of two components. A & B may be given as PA = PoA XA and PB = PoB XB And total pressure P is given by P = PA + PB = PoA XA + PoB XB The ideal solutions also have the following characteristics 1. Heat change on mixing is zero or Δ Hmix = 0. There is no change in magnitude of attractive forces in the two components present as A and B. 2. Volume change on mixing is zero or Δ Vmix = 0 The properties of an ideal solution are the average of the properties of the components present as per their mole fraction. If an ideal solution having components A and B in equal number of moles, then solution will have vapour pressure exactly midway between the vapour pressure of A and B. An ideal solution will be formed only when the components or substances composing them are similar in structure and polarity. If two liquids A and B form an ideal solution this means that force of attraction between A and B molecules i.e. A - B molecular interaction force is similar to the force of attraction between A - A or B - B molecules. Liquid Hexane (C6H14) and Heptane (C7H16) when mixed in any proportion, form nearly ideal solution. A perfect ideal solution is rare but many solutions are nearly ideal in behaviour. Here nearly ideal solution means a very small deviation from Raoult's equation. Example of ideal solution i) Hexane and Heptane, ii) C2H5 Br and C2H5I, iii) C6H6 and C6H5 - CH3, iv) C6H5Cl and C6H5 Br. Generally all the solutions tend to become ideal when they are dilute

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
Non - ideal solutions The solutions which do not obey Raoult's law are called non ideal solutions. For non ideal solution following conditions are there i. PA # PoA XA, PB # PoB XB ii. Enthalpy change on mixing Δ Hmix # 0 iii. Volume change on mixing Δ V # 0

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Types of non- ideal solutions
They are of two types a. Non Ideal solutions showing positive deviations from Raoult's law. b. Non Ideal solution showing negative deviations from Raoult's Law. a. Non ideal solutions showing positive deviations from Raoult's law Suppose we are preparing a solution by two components A and B. If the interaction between A and B (A---B) in the solutions are weaker than the interaction between A - A and B - B, then the escaping tendency of A and B types of molecules from the solution becomes more than from pure liquids. As a result of this the partial vapour pressure of each component will be greater than the expected on the basis of Raoult's law. The total vapour pressure of solution will be greater than the vapour pressure as per the Raoult's law.

In the above figure, we see that total vapour pressure P is greater than expected. The dotted line is expected vapour pressure. The above type of behaviour of solution is described as positive deviation from Raoult's law. Mathematically we may express as PA > PoA XA PB > PoB XB and total vapour pressure P = PA + PB is always greater than PoA XA + PoB XB For the solutions which show positive deviations, there is an intermediate composition of components for which the vapour pressure is maximum and hence, boiling point will be minimum. For such composition the solution having minimum boiling point and it will distil at a particular temperature without change in composition. A solution which distils without change in composition at a particular temperature is called Azeotropes or Azeotropic mixture. The azeotropic mixture showing positive deviations is called minimum boiling azeotrope.

Explanation for positive deviations
Suppose we are preparing an solution of ethyl alcohol and cyclohexane. In ethyl alcohol, molecules are held together by hydrogen bonds as shown below

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES

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When cychlohexane is added to ethyl alcohol, the molecules of cyclohexane tend to occupy the spaces between ethyl alcohol molecules. So some hydrogen bonds in alcohol molecules break and the attraction forces in alcohol molecules is weakened. The escaping tendency of alcohol and cyclohexane molecules from the solution is greater than the vapour pressure as expected by Raoult's law. Solutions, which are showing positive deviation, they will have 1. H mixing > 0 or positive because energy is required to break A ---- A or B ----- B attractive forces. Therefore making solution will be endothermic process. 2. As the molecules are loosly held in the solution, there will be increase in volume on mixing. Δ V mixing > 0 or positive. b) Non - ideal solution showing negative deviations In this type of deviation the partial vapour pressure of each component of solution is less than the vapour pressure as expected according to Raoult's law. In such solutions (component A and B), the A ---- B interactions are stronger than the A --- A and B-----B interaction. Due to stronger A ----B interaction, the escaping tendency of A and B types of molecule from the solution becomes less than from pure liquids. Each component of solution has a partial vapour pressure less than expected on the basis of Raoult's law and total vapour pressure becomes less than the corresponding vapour pressure expected in case of ideal solution.

Here PA < PoA XA and PB < PoB XB P = PA + PB is always less than PoA XA + PoB XB Δ H mixing < 0 or negative Δ V mixing < 0 or negative.

Explanation for negative deviations
We will take the example of solution prepared by mixing acetone and chloroform. When they are mixed, there will be a attractive force between the molecules as shown under

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES

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The new type of force which is acting between the molecule is hydrogen bonding. Vapour pressure of solution will be less than expected for an ideal solution. Here Δ Vmixing < 0 because energy is released due to increase in attractive forces. Dissolution process is exothermic and heating the solution will decrease the solubility. Δ Vmixing < 0 because molecules are held together more strongly and so there will be decrease in volume. For the solution with negative deviation there is an intermediate composition for which vapour pressure of the solution is minimum and hence boiling point is maximum. At this composition the solution distil at constant temperature without the change in composition. So it is an azeotrope. The solutions which show negative deviations from Raoult's law are also called maximum boiling azeotropes. Table - non ideal solutions Solution showing positive deviations 1. (CH3)2CO + CS2 2. (CH3)2CO + C2H5OH 3. C6H6 + (CH3)2 CO 4. CCl4 + C6H6 5. CCl4 +CHCl3 6. CCl4 + C6H5CH3 7. H20 + CH3OH 8. H20 + C2H5OH 9. CH3CHO + CS2 10. CHCl3 + C2H5OH Solution showing negative deviation 1. CH3COOH + C5H5N (Pyridine) 2. CHCl3 + (CH3)2 CO 3. CHCl3 + C6H6 4. CHCl3 + C2H5 - O - C2H5 5. H2O + HCl 6. H20 + HNO3 7. (CH3)2CO + C6H5NH2

Abnormal molecular masses
Collegative properties are used for the determination of molecular masses of the solute. We are familiar with the formulas, which has been derived in Relative lowering of vapour pressure, elevation in boiling point, depression in freezing point and osmotic pressure. Relation between all the above collegative properties and molecular mass of the solute is based on the following two assumptions. 1. The solution is dilute so that Raoult's law is obeyed. 2. The solute neither undergo dissociation not association in solution. If the above assumptions are not valid in a solution, we will find discrepancies between the observed and calculated values of Collegative property. Reason of discrepancies will be discussed in two heads 1. association of solute molecules 2. dissociation of solute molecules 1) Association of solute molecules In certain solvents generally non polar, the solute molecules undergo association. Two, three or even more molecules exist in combine state and form a bigger molecules n A ---------------------------------> An n single molecules one molecule

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
Therefore, the total number of molecules in solution become less than the number of molecules of the substances added. So, colligative properties will be lower. Colligative property is directly proportional to the number of solute particle and inversely proportional to the molar mass of the solute. i.e. Colligative property α ( 1 / molecular mass of solute )

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Here, molecular masses of solute will come greater than theoretical values. Let we take an example of acetic acid and Benzoic acid dissolved in Benzene. Both acids exist in dimer form 2CH3COOH (CH3COOH)2 2C6H5COOH (C6H5COOH)2 The association of solute molecules in a solution is generally due to hydrogen bonds between these molecules.

Acetic acid dissolved in Benzene shows a molecular mass 120 (Normal Molecular Mass 60) and Benzoic acid dissolved in Benzene is found to have molecular mass double of its normal molecular mass. It is only due to formation of dimer of acetic acid and benzoic acid in Benzene. Here number of particles (solute) will be half of the number dissolved because of association. As a colligaive property depends upon the number of particles and not of their nature, Δ T value for benzoic acid dissolved in benzene will be half of the normal value. The molar mass calculated on the basis of this Δ T will, therefore, be twice the expected value. 2) Dissociation of solute molecules A number of electrolytes dissolved in solvent dissociates. If we dissolve KCl. After dissociation of KCl, we get K+ and Cl- ions. For some other electrolytes we may get more than two ions also. Therefore, the number of solute particles in solution will be more than expected. Such solutions exhibit higher values of colligatives properties. Δ T value of such solution will be twice due to increase of number of particle as it has become double. Since, colligative property are inversely proportional to the molecular masses, therefore molecular masses of such substances as calculated from colligative properties will be less than their normal values. For KCl KCl K + + Cl -

Since each KCl unit is dissociated into two ions, the molar mass of KCl will come half of its Normal Molar mass. Van't Hoff factor In 1886, Van't Hoff introduced a factor (i) called Van't Hoff factor to express the extent of association or dissociation of solutes in solution. It is ratio of the normal and observed molecular masses of the solute i.e. i = (Normal molecular mass / Observed molecular mass ) In case of association, observed molecular mass being more than normal, the factor i has value less than one but in case of dissociation, the Van't Hoff factor is more than one because observed molecular mass has a lesser value than the normal molecular mass. If there is no association or dissociation, i is one.

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
i=1 i>1 i<1 No association or dissociation of solute Dissociation of solute Association of solute

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Since, colligative properties are inversely proportional to molecular masses, the Van't Hoffs factor may also be written as i = ( Observed value of colligative property / Calculated value of colligative property assuming no association or dissociation ) or i = ( No. of particles after association or dissociation / No. of particle before association or dissociation ) Inclusion of the Van't Hoff factor modifies the equation for the colligative properties as follows iii. iv. v. vi. (PoA - PA) / (PAo) = i xB Δ Tb = i kb m Δ Tf = i kf m π = icRT

Degree of dissociation It is defined as the function of total molecules which dissociates into simpler molecules or ions. Suppose a molecule of an electrolyte gives m ions after dissociation. If we are taking 1 mole of electolyte and α is the degree of dissociation, then at equilibrium.

Number of moles of ions formed = m α Number of mole of solute left undissolved = 1 - α Therefore, Total Number of moles of particle at equilibrium = 1- α+m α Therefore, Vant's Hoff factor i = ( Total no. of particle after dissociation / No. of particle before dissociation ) i = ((1 - α ) + m α / 1 ) = 1 + (m - 1) α Therefore, (m - 1) α = i - 1

α = ( i - 1 / m - 1)
For the electrolyte of type AB, such as KCl, NaCl, NaOH etc. the number of particle in solution i.e. m = 2. Therefore, α = i - 1 = ( i - 1 / 2 - 1 )

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
For the electrolyte of type AB2 like CaCL2, Ba (NO3) 2 etc. The value of m = 3 so α =i-1/3-1=i-1/2

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Degree of association. It is defined as the fraction of total number of molecules, which associate or combine together resulting in the formation of a bigger molecules. Degree of association = ( No. of moles of substance associated / Total no. of moles of substance taken ) In order to calculate the degree of association, suppose that m particles of solute associate to form one particle and α is the degree of association as given in the following equation mA -----------> Am In mA No. of moles in the beginning = 1 moles No. of moles after association = (1 - α ) Moles In mA No. of moles in the beginning = 0 moles No. of moles after association = α / m moles Here α molecular are going to associate, then α / m molecules will be formed due to association. Therefore, Total no. of Moles after association = ( 1- α + α / m) Moles. Therefore, Van't Hoff factor = ( No. of particles or moles after association / No. of particle or mole before association ) i=(1- α + α/m)/1=1- α+ α/m

α/m- α=i-1 α (1/m - 1) = i - 1
Therefore, α = i -1 / ( 1/ m - 1 )

Numerical problem
1) Benzene (C6H6) with B.P 353.1 k and toluene (C6H5 - CH3) with BP 383.6 k are two hydrocarbons which form nearly ideal solution. At 313 k, the vapour pressure of pure benzene and pure toluene are 160 mm of Hg and 60 mm Hg respectively. Calculate the partial pressures of C6H6 and C6H5 - CH3 and the total pressure under the following condition i) A solution made by mixing equal number of moles of 8H6 and C6H5-CH3

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
ii) A solution made by mixing 4 moles of toluene and 1 mole of Benzene. iii) A solution made by mixing equal masses of toluenes and Benzene. Solutions i) Suppose a moles of Benzene and a moles of toluene are mixed up. Therefore, Mole fraction of Benzene = a / a + a = .5 = XA and mole fraction of toluene = 1-.5 = .5 = XB We know PA = PoA XA Where PA is the partial V.P. of Benzene in the solution. And PoA is the V.P of Pure Benzene. Therefore, PA = 160 x .5 = 80 mm. And PB = PoB XB Where PB is partial VP of Pure Toluene Therefore PB = 60 x .5 = 30 mm Total vapour pressure (VP) = 80 + 30 = 110 mm Hg. ii) a mixture of 4 moles of toluene and 1 mole of Benzene therefore; Mole function of Benzene = ( 1 / 4+1 ) = ( 1 / 5 ) = .2 = XA and Mole fraction of toluene = 1 -.2 = .8 = XB We know PA = PoA XA PA = 160 x .2 = 32 mm so partial vapour pressure of Benzene is 32 mm. also PB = P0B XB = 60 x .8 = 48 mm partial V.P of toluene is 48 mm. Total V.P = 48 + 32 = 80 mm of Hg iii) Suppose x gm of Benzene and x gm of toluene are there in the solution Therefore, No. of moles of Benzene = ( X / 78 ) molecular wt. of Benzene is 78 and No. of moles of Toluene = ( X / 92 ) molecular wt. of toluene is 92 Mole fraction of Benzene XA = x/78 / ( X/78 + x/92 ) = 0..541 Mole fraction of Toluene XB = 1 - .541 = 0.459 partial vapour pressure of Benzene PA = PoA XA = 100 x .541 = 86.56 mm partial vapour pressure of Toluene PB = PoB XB = 60 x .459 = 27.54 mm Total Vapour Pressure = 86.56 + 27.54 = 114.10 mm of Hg.

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Q.No.2. The vapour pressure of a dilute aqueous solution of glucose (C6H12O6) is 750 mm of mercury at 373 k. Calculate (I). Molality, (ii). Mole function of the solute (IIT - 1989) Soln. 1. Suppose molality of the solution = i x. It means x moles of glucose is dissolved in 1000 gm water. here no. of moles of glucose = x and no. of moles of water = ( 1000 / 18 ) = 55.55 here VP of water at 373 k is 760 mm we know ( PoA - PA / PoA ) = XB here mole function of solute = ( x / x + 55.55 ) Therefore ( 760 - 750 / 760 ) = ( x / x + 55.55 ) ( 10 / 760 ) = ( x / x + 55.55 ) 760x = 10 x + 555.5

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Notes by ROHIT DIXIT for the students of DIXIT CHEMISTRY CLASSES
750 x = 555.5 x = ( 555.5 / 750 ) = .74 Mol Kg-1 II. Here Mole fraction of solute Glucose = x / X + 55.55 = ( .74 / .74 + 55.55 ) = .74 / 56.29 = .013

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