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Volumetric Analysis (Acidimetry & Alkalimetry)

1. Titration : Titration is a process by means of which the concentration (strength) of a solution determined by allowing to react with a standard solution.
2. Acidimetry : It is the process by which strength of an acid is determined by reacting with a known amount (standard solution) of base in the presence of an indicator.
3. Alkalimetry : It is the process by which strength of an is alkali determined by reacting with a known amount (standard solution) of acid in presence of an indicator.
4. Standard Solution : A solution of definite concentration is called a standard solution. That is by standard solution we mean that a known amount of solute is dissolved in a given volume of solution. As an example 10gm of NaCl dissolved in 200ml solution is a standard solution.
5. Neutralization : The process of complete reaction of hydrogen ions of an acid with the exact amount of hydroxide ions of an alkali to form alkali molecules is called neutralization.It should be noted that neutralization does not mean that the resulting solution is always neutral. i.e. PH = 7 . In fact, when the same value of equivalent amount of acid and alkali reacts, it is said neutralization process has taken place.
6. Indicators : Indicators most frequcency used in acid base titration are methyl orange and phenolphthalein. Indicators are substance by which change colour and without reacting with solution indicate the end point we mean that equivalent amounts of substances have reacted.
Indicators also indicate whether a given solution is alkaline or neutral.

7. Some commonly used indicators and their PH Range :
Indicator                     Colour in A Med.            Colour in B. Med.            Pá´´- Range
Methyl Orange                    Red                                   Yellow                          3.4 – 4.7
Phenolphthalein                  Colourless                            Pink                            8.2 – 10
Methyl Red                         Red                                    Yellow                         4.2 – 6.3
Litmus                                 Red                                     Blue                           5.5 – 8.0
Thymol blue base                Yellow                                 Blue                            8.0 – 9.6 

8. The choice of indicator in acid-alkali neutralization:
Acid           Alkali        PH-Range          Indicator       Solution in burette
Strong              Strong                  4 to 10            Ph. or M.Or. or litmus              Alkali
Strong              Weak                   3.5 to 7                M.Or. or M.R.                    Acid
Weak               Strong                 6.5 to 10                      PH                             Alkali
Weak               Weak                   No Sharp                    None           

9. Equivalent weight of some substance
         It is hoped that students are quite familiar with definitions of equivalent weight of acid, alkali, compound and salt. The equivalent weight of few substance are noteworthy Compound wt.                           Mol. Weight                     Equivalent HCl                                              36.5                                    36.5 HNO3                                           63.0                                   63.0 H2SO4                                           98.0                                 49.0 H2C2O4.2H2O                              126.0                                63.0 NaOH                                            40.0                                 40.0 KOH                                              56.0                                 56.0 CaO                                               56.0                                 28.0 Na2CO3.10H2O                             286.0                               143.0 Na2CO3                                         106.0                               53.0 NaHCO3                                        84.0                                 84.0 CaCO3                                           100.0                               50.0 MgCO3                                          84.0                                 84.0 NaCl                                              58.5                                 58.5 AgCl                                             143.5                                143.5 AgNO3                                          170.0                                170.0 BaSO4                                            233                                  116.5 NH4Cl                                            53.5                                  53.5 NH3                                                 17                                     17 10.     Concentration of Strength of solution
Relative amount of the solute and the solvent present in the solution. It is expressed in different units given below.
i.    Percentage strength          %(v/v),%(w/v) or %(w/w)
ii.    Gram per litre                               g/l
iii.    Normality                                     N
iv.    Molarity                                       M
v.    Molality                                        M
vi.    Mole Fraction                              X


i. Percentage strength :
a.     % by volume (w/v) :
It means that the weight of solute in grams dissolved per 100ml of its solution. Thus 2% NaCl solution means that 2gm NaCl is dissolved per 100ml of its solution.
% by volume =
Weight of solute (in gm) × 100
Volume of solution (in ml)
b.     % by weight (w/w) :
It express the weight of solute in grams dissolved per 100gm of its solution. As an examples 5% Na2CO3 by weight means that 5gm of Na2CO3 is displayed per 100gm of its solution.
% by weight =
 Weight of solute  ×100
   Volume of solution

ii. Gram per litre (g/l) :
The term itself implies the weight of solute in grams dissolved per litre or 100ml of its solution.
Gram per litre =
 Weight of solute (in gm)
 Volume of solution (in l)
         
 Weight of solute (in gm) × 1000
Volume of solution (in ml)

    iii.      Normality :
It is the number of gram equivalents of solute dissolved per litre solution. The numerical value is following by the letter N.
Thus 0.5 N solution means that the normality is 0.5, It than follows that 0.5 gram equivalent of solute is present in 1 L of solution.
Normal solution (1N) : it is the solution containing one gram equivalent of solute dissolved per litre of its solution.
Semi normal solution (N/2) : It is the equation containing half of the gram equivalent of solute per litre solution.W =
N(normality) × E(Eq. wt) ×V(ml)
                    1000
   iv.      Molarity :
It is the number of g-molecules (moles) of solute dissolved per litre its solution. As shown for normality, molarity, M =
W ×1000
V × MW
Where Mw is the molecular wt. of solute.
Molar solution (1M) : It is the solution containing one gm- molecule of the solute dissolved per litre solution.
v. Molality :
Molality is the number moles of the solute dissolved per 1 Kg or 1000gm of solvent.
If ‘a’ gm of solute of molecular weight MW is dissolved in “b” gm of solvent, then by definition, Molality =
a × 1000
MW × b
vi. Mole Fraction :
Mole fraction of a component in a solution is the ratio of the number of moles of that component and the number of moles of all the components in solution.
If a solution is prepared by dissolving nx mole of solute in ny mole of solvent, then
Xsolute = nx/(nx + ny)
Xsolvent = ny/(nx + ny)
Obviously; Xsolute+ Xsolvent = 1.0
11. Important :
- The most common mode of expressing concentration of a solution is molarity.
- Since mass does not change with rise in temperature, the value of molality, and mole fraction remains the same.
- As there in increase in volume by increase of temperature, the value of molarity and normality decreases when temperature is increased.
- When a certain volume of a standard solution is diluted (i.e. the volume is increased by addition of water) the concentration decreases.
- Normality and molarity of a solution is related as
Normality = molarity × mol. wt./eq. wt.
12. Normality factor :
It is the ratio of the weight of solute taken and the wt. of the solute required to prepare a solution of a particular strength.
Suppose 1.3gm of Na2CO3 is dissolved in 250 ml of a solution to prepare N/10 Na2CO3.By calculation the weight of Na2CO3 required = (250×53)/(10×1000) = 1.325 gm
Hence, by definition normality factor of N/10 Na2CO3.
Solution = 1.3/1.325= 0.98
The strength of solution =N/10 , (f = 0.98)
13. Basic principles of calculation :
1. When two solutions containing different solutes are able to different solutes are mixed and are to react together, it is the solutes present that react with themselves, water just speeds up the reaction.
2. Solutes completely react and products there by formed in a given reaction are always in proportion to their gm-equivalent.
3. If V1ml of a solution of strength N1 react completely with V2 ml of another solutes of strength N2, then their number gm-eq. of solute is
V1× N1 = V2× N2
4. Strength of a mixture : when different solution of the same nature and of given volume and strength are mixed, the principles (2) still holds
That is VmNm = V1N1+ V2N2+ V3N3+……………………….
When all solution are acids or alkalies, The subscript m stands for mixture, When acids and alkalies are mixed
VmNm = V1N1+ V2N2  _  V1N1+ V2N2  ……………………
                 Acids              Alkalies
5.     Acids and alkalies of the same strength in terms strength in terms of normality require the equal volume for neutralization.
Important formulae:
1. Strength in percentage = (gm/lit)/10.
2. Required amount (w) = (NEV)/1000.
3. Normality (N) = [(w/w)% × SP. gr × 10 ]/[eq. weight.]
4. Molarity (M) = [(w/w)% × SP. gr × 10 ]/[mol. weight.]
5. Normality (N) = [(w/v)% × 10 ]/[eq. weight.]
6. Molarity (M) = [(w/v)% × 10 ]/[mol. weight.]
7. N1V1 = N2V2
8. S1V1 = S2V2(only for dilution)
9. NV = N1V1+ N2V2+ N3V3
10.  M1V1 × Basicity = M2V2 × Acidity.



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