1 8.

1 Solution, Atom fraction, Mole fraction, Molality, Molarity and Normality

A solution is a homogeneous mixture composed of two or more substances. In the study of solutions, it is customary to designate the component present in larger proportion as the solvent and the one in smaller proportion as the solute. A common example of solution is salt or sugar, dissolved in water. Examples of solid solutions are alloys, The physical properties of compounds such as melting point and boiling point change when other compounds are added. The Concentration of a Solution refers to the amount of the solute present in a given amount of solvent or solution.There are several ways to quantify concentration of a solution. Examples include Atom fraction, Mole fraction, Molality, Molarity and Normality etc. To define the above methods used to express the concentration of solute consider a binary (means having two components) solution in which solvent is represented by A and solute by B then 1) Atom fraction of A is defined as

No.of moles of A Atom fraction of A = No.of moles of A 2) Atom fraction of B is defined as + No.of moles of B

No.of moles of B Atom fraction of B = No.of moles of A 3) Mole fraction of A is defined as + No.of moles of B

No.of moles of A Mole fraction of A = No.of moles of A 4) Mole fraction of B is defined as + No.of moles of B

No.of moles of B Mole fraction of B = No.of moles of A 5) + No.of moles of B

Molarity : molarity is defined as no.of moles of solute dissolved in one litre of solution. Molarity is represented by M

No.of moles of B M That is = Volume of the solution in Litres

No.of moles of B

weight of B = Molecular weight of B

6)

Molality : molality is defined as no.of moles of solute dissolved in kilogram of solute molaity is represented by m

No.of moles of B m That is = Mass of solvent in kgs

7)

Normality : Normality is defined as no.og gram equivalents of solute dissolved in one litre of solution normality is represented by N

No.of gram equivalents of B N = Volume of solution in litres

3 That is

8.2

CLASSIFICATION OF SOLUTIONS

Depending on the behaviuor of solutions they are classified as 1) Ideal solutions 2) Real solutions and 3) Regular solutions 1) Ideal solutions : A Solution is called ideal solution if the interactions between similar and dissimilar atoms is the same that is in an ideal solution of A and B, the A-A, B-B and A-B interactions are identical Or FA-A = FB-B = FC-C Where F indicates the interaction Example: Cu-Ni alloys For an ideal solution Hmix,ideal = 0 Smix,ideal 0 Vmix,ideal = 0 2) Real solution : A Solution is called real solution if the interactions between similar and dissimilar atoms is different that is in a real solution of A and B, the A-A, B-B and A-B interactions are different Or FA-A FB-B FC-C Where F indicates the interaction For a real solution Hmix,real 0 Smix,real 0 Vmix,real 0 Example: Fe-Ni, Fe-Cu 3) Regular solution : A special type of a non-ideal or real solution whose behaviour is in between the ideal and real solutions for which the enthalpy of mixing is non-zero but the entropy of mixing is identical to that of ideal solutions For a regular solution Hmix,reg 0 Smix,reg = Smix,ideal Vmix,reg 0 8.3 RAOULTS LAW FOR IDEAL SOLUTIONS

Raoults law : The activity of a component of an ideal solution is equal to its mole fraction. That is in an ideal solution of solvent A and solute B, Where Activity of A Mole fraction of A

4 Similarly Where XB 8.4 ACTIVITY COEFFICIENT aB = XB aB Activity of B Mole fraction of B

Activity Coefficient : The ratio between Activity to mole fraction of a component in a solution is called Activity coefficient and is represented by and is written as follows

=a/X
We can quantify the deviation of a solution from ideality by using the activity coefficient In an ideal solution of A and B, the A-A, B-B and A-B interactions are identical and Hence a A = XA (here A = 1) When, A-B interactions are stronger than A-A or B-B interactions; Then a A < XA (here A is < 1 (negative deviation from ideality) system can then tend towards compound formation and mixing is exothermic. Example: Fe-Ni (liquid alloy); When A-B interactions are weaker than A-A or B-B interactions; then A is > 1 (positive deviation from ideality), system can then tend towards phase separation and mixing is endothermic. (Example: Fe-Cu liquid alloy). 8.5 FACTORS CAUSING DEVIATIONS FROM IDEAL BEHAVIOUR The deviations of a real solution from ideal behaviour are of two types they are 1) Positive deviation and 2) Negative deviation The factors which cause the deviations are the interactions between similar and dissimilar atoms of the components of the solution. Consider a solution in which the solvent is A and solute is B and if the interactions between similar atoms are F A-A and FB-B and the interactions between dissimilar atoms are FA-B then 1) If FA-A = FB-B = FA-B Then the solution becomes ideal

5 2) If FA-A < FA-B > FB-B deviation 2) If FA-A > FA-B < FB-B Then the solution under goes positive deviation Then the solution under goes negative

The deviations are shown below in the diagram

8.6

DILUTE SOLUTION AND HENRYS LAW

Dilute Solution: is one in which a relatively small amount of solute is dissolved in the solvent. All gases are dissolved to a certain extent by all liquids, the amount dissolved depending upon the pressure, the temperature, the nature of the gas and the nature of the solvent. Thus pressure has a marked influence on the solubility of a gas in a given solvent. Henry (1803) discovered a very simple relation between the pressure and solubility of a gas. This relation called Henry's law may be stated as:

6 The solubility of a gas in a given solvent is directly proportional to the pressure to which the gas is subjected, provided the temperature remains the same i.e. S P or S =k P Or Henry's law may be defined alternately as the following The activity of solute of a dilute solution is directly proportional to the mole fraction of the solute i.e.

aB = B XB
Where

aB Activity of solute B B Law constant XB Mole fraction of solute B

8.7

SIEVERTS LAW

Definition Sieverts Law can be stated as the solubility of a diatomic gas in a molten metal is directly proportional to the square root of the partial pressure of the gas. That is S = K P Where S --- is the solubility of the gas in the molten metal K--- Proportionality constant P--- Partial pressure of the gas For a diatomic gas like nitrogen the law can be written as S = K PN2 Where PN2 --- the partial pressure of Nitrogen According to Sieverts law the solubility of a gas in a molten metal depends on the atomicity of a gas. For instance the solubility of a tri atomic gas the law becomes as the following S = K 3P That is the solubility is directly proportional to the cube root of the partial pressure of the gas

7 Similarly for the nth atomic gas the law can be written as S = K nP Applications 1) To assess the solubility of gases in molten metals 2) To assess the gas (such as nitrogen etc) dissolution in molten weld metal during welding