Department of Applied Chemistry

Practical Manual

SHRI RAMDEOBABA KAMLA NEHRU ENGINEERING COLLEGE, NAGPUR

CHEMISTRY PRACTICAL MANUAL

INDEX Expt. No 1 2 Name of the Experiment. To determine alkalinity of given water samples. Determination of hardness of water by Complexometric method 3 To estimate the amount of Copper in given solution by Iodometry. 4 5 Determination of Chlorine in given water sample. To estimate the amount of Ferrous and Ferric ions present in the given solution. 6 Determination of viscosity of a given sample at different temperatures. 7 Determination of Flash Point of given sample by Abels Flash Point apparatus. 8 Determination of Flash Point of given sample by PenskyMartens flash point apparatus 9 Determination of Flash Point of given sample by Clevelands Flash Point apparatus. 10 Determination of Chemical Oxygen Demand in a given wastewater sample. 11 12 Determination of Acid Value of given sample. Determination of Saponification Value of a given sample. 46-48 49-52 41-45 39-40 36-38 33-35 27-32 19-22 23-26 14-18 Page No. 02-05 06-13

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EXPERIMENT NO. 1
Aim: To estimate the Type and Extent of alkalinity present in the given water sample Principle: The alkalinity of a water sample is due to carbonates (CO32-), bicarbonates (HCO3-) and hydroxide (OH-) ions. Thus in a given water sample the possible combination of ions causing alkalinity are as follows. (i) OH - alone (ii) CO3 2 - alone (iii) HCO3 - alone (iv) OH- and CO32 together (v) CO32-and HCO3- together The possibility of OH- and HCO3-ions together in the same solution is ruled out as they react asHCO3 - + OH is ruled out. The determination of alkalinity involves following reactions. OH- + H+ CO3 2-+ H+ HCO3- + H+ H2 O HCO3----------------1)
-

CO3 2 -- + H2O

In the same way, possibility of co -existence of all the three OH- , CO32-and HCO3 -

---------------- 2)

H2CO3

H2O + CO2 ---------------- 3)

The phenolphthalein is pink in color above pH 10 and it is colorless below pH-8. While, The methyl orange is yellow above pH 4.4 and it turns pink below pH 3.1

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Department of Applied Chemistry

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Thus titration of a given water sample in presence of phenolphthalein as an indicator indicates completion of reaction 1 and 2 whereas the same water sample, if titrated in presence of Methyl orange as an indicator indicates the completion of reaction 1,2 and 3. The water sample, when titrated with an acid solution using phenolphthalein indicator gives (End point = P) and with methyl orange indicator gives (End point = M). The relation between P and M points gives the type and extent of alkalinity is established as follows:

Relation between P&M point P =M P = 1/2 M P=0 P>1/2 M P<1/2 M

Type of alkalinity Only OHOnly CO3 -Only HCO3OH-&CO3-CO3-- & HCO3-

Extent of alkalinity OHM (2P-M) CO322P 2(M-P) 2P HCO3M (M-2P)

Procedure: Part 1: - Determination of type of alkalinity. Take 25-ml. water sample in a conical flask. Add 1-2 drops of phenolphthalein as an indicator. The solution becomes pink. Titrate this solution with acid solution from the burette. At the end point the pink color of the solution changes to colorless. Note this end point as P point. Now At this point, add 2 drops of methyl orange indicator to the same solution. Solution becomes yellow. Again titrate the solution with same acid solution from the same burette. The end point may be obtained immediately or after addition of some amount of acid. In the former case, obviously, P = M and in later P M. The relationship between P point and M point denotes the type of alkalinity present in the given water samples as shown in earlier table.

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Department of Applied Chemistry Calculations:-

Practical Manual

Part 1 : Determination of type of alkalinity present in water sample A The given Normality of HCl solution is = N1 and If P > 1 / 2 M then, The type of alkalinity present in given water sample is OH- and CO32Now, 1)Volume of acid corresponding to OH - = 2P- M 2) Volume of acid corresponding to CO32- = 2 (M- P) a) Normality of water sample due to OHHCl N1V1 = N1 x 2P- M N2 = ------------------25 Wt/ lt for OH- = Normality x Eq. Wt.of CaCO3 = = = = N2 x 50 g/l x 1000 mg/l ppm Water sample A N2V2

b)Normality of water sample due to CO3 2-. HCl N1V1 = N1V1 x N3 Water sample A N3V3 2 (M- P)

= ------ -------------------25

Wt./ lt for CO3 2-.

= = = = =

Normality N3

x Eq.. Wt. of CaCO3 x 50 g/l x 1000 mg/l ppm

Same calculations are to be carried out for Water sample C Shri Ramdeobaba Kamla Nehru Engineering College, Nagpur 4

Department of Applied Chemistry Result: The given water sample A contains:OH Alkalinity CO3
2

Practical Manual

= ------------ ppm = ------------- ppm = ------------- ppm

Alkalinity

Total Alkalinity

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Department of Applied Chemistry

Practical Manual

EXPERIMENT NO. 2
Aim : Determination of hardness of water by comlexometric method. Principle: Complexometry involves the interaction of an organic compound with a

complexable metal ion and results in the formation of compounds known as Werners complexes. The organic compound is an anion or a Lewis base and is known as Ligand. Several factors, such as pH, basicity of ligand, type of ring formed etc. govern the successful formation of a complex. Thus: XL Ligand + M n+ --------(L) x M Complex

Metal ion

Ethylene diamine tetra acetic acid (EDTA) is a well known complexing agent which is widely used in analytical work on account of its powerful complexing action and commercial availability.

HOOC-H2C \ N-CH2-CH2-N / HOOC-H2C EDTA \ /

CH2-COOH

CH2COOH

The spatial structure of its anion which has six donor atoms , enables it to satisfy the coordination number of six, frequently encountered among the metal ions and to form strain less five membered rings on chelation.
2+ 2+ 2 +

EDTA forms complexes with Ca

, Mg

, Zn

as well as with many other metal

ions in an aqueous solution. The complexes have the general formula.

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Department of Applied Chemistry

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O O O

O
2+

M
H 2C N H2 C O O H2 C

CH 2 H2 C N CH 2 O O

Structure of Metal-EDTA Complex EDTA is generally used in the form of disodium salt or tetra sodium salt on account of their greater solubility. For simplicity of discussion, EDTA is assigned the formula H
4

Y, the

disodium salt will hence be Na 2 H2 Y which gives the complex forming ion H2Y 2- in aqueous solution. It reacts with metal ions in 1:1 ratio. The reaction with divalent cations, M 2+ (Such as Mg 2+ or Ca 2+) may be represented as, M2+ + H2 Y2 MY 2- + 2H +

-----------

Thus it is evident that 1 mole of the complex forming H2 Y2 - reacts in with one mole of the metal ion and, two moles of hydrogen ions are generated. It is apparent from the equation above that the dissociation of the complex will be governed by the pH of the solution. Lowering of the pH will decrease the stability of the metal EDTA complex. .

INDICATOR: Metal ion indicators are commonly used in EDTA titrations. Eriochrome blackT, also known as EBT or Solochrome black is the metal ion indicator used for complexometric titration. Eriochrome black-T is 3-hydroxy,4(1-hydroxy, 2 -azo napthyl), 7-nitro 1 sodium napthyl sulphonate.

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Department of Applied Chemistry

Practical Manual

HO OH

NaO 3S

O2N

Structure of EBT Indicator This compound tends to polymerize in strongly acidic solutions to a red brown product and hence this indicator is used in EDTA titrations with solution having pH greater than 6.5. This EBT posses three replacable hydrogen atoms, one from sulphonic acid group and two form phenolic OH groups. The sulphonic acid looses its proton to form Na salt, as it is more acidic than the other groups. The dissociation of the two hydrogen atoms of phenolic groups only should therefore be considered and hence EBT for the simplicity is represented asNaH2D which gives H2D ion which exhibits different colours at different pH values. H2D - ----------pH 6.3 H D 2- ------------pH 10 D3pH 11.5

( Red)

(Blue)

(Yellowish Orange)
2-

In the pH range 8-10, the blue form of the indicator HD complex with Metal ion. For ex.: Mg 2+ + HD2- ---------Blue Mg D- + H+ Wine red

gives a wine red

Now, if EDTA is added to such a solution, Mg 2+ / Zn2+ preferentially complexes with EDTA (since the metal-EDTA complex is more stable than the metal indicator complex)

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Department of Applied Chemistry

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and liberates the free indicator HD2- at the end point, thereby producing a sharp colour change from wine red to blue. The hardness producing constituents of water i.e. Ca2+ and Mg2+ can be estimated by titrating with Ethylene diamine tetracetic acid (EDTA) which acts as the ligand, using Ericromic Black-T as an indicator, which as explained above is also a ligand. In the pH range 8-10, the indicator is blue and forms a wine red coloured complex with Ca2+ / Mg2+ ions. In this estimation, thus four types of complexes are possible viz : a) EBT Mg2+ complex b) EBT - Ca complex c) EDTA- Mg2+ complex d) EDTA- Ca2+ complex
2+

(Wine red) (Wine red) (colourless) (colourless )

Their order of stability and consequently, their preference of formation are: EDTA- Mg2+ > EDTA- Ca2+ > EBT Mg2+ > EBT Ca 2+

The colour and stability of these complexes is made use of in the estimation of hardness of water using EBT and EDTA in the complexometric methods. To a known volume of hard water(say 25 ml) containing Ca2+ and Mg2+ , are added 2-3 drops of EBT at a pH of 8-10, maintained with the help of ammonia buffer. The EBT forms a wine red complex with Mg2+. EDTA is then added when it first reacts with the free Mg2+ then with free Ca2+ and finally after all the free metal ions are exhausted, it reacts with the EBT- Mg2+ complex, extracting the Mg2+ ions (as EDTA-Mg2+ complex is more stable than EBT-Mg2+ complex). In this way, the free EBT ion (HD2-) is generated which being blue in the pH range 8-10, imparts a blue colour to the solution. Thus the colour change at the point is wine red to blue.

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Department of Applied Chemistry Reactions:

pH

Practical Manual

EBT + Mg2+ -------8-10

EBT-Mg2+ Complex (Wine red colour obtained)

pH EDTA + Mg2+ -------8-10 EDTA- Mg2+ complex (Colourless)

pH EDTA + Ca2+ -------8-10 EDTA + EBT-Mg 2+ complex (Wine red) EDTA-Mg 2+ complex EDTA-Ca2+ complex (Colourless)

---------PH 8-10

EBT ( blue)

PROCEDURE: Part 1: Standardisation of EDTA Take 25 ml.of standard hard water sample in a clean conical flask. To it add 2 ml of buffer solution (NH4Cl + NH4OH) and 3-4 drops of indicator EBT. The solution becomes wine-red in colour. Titrate this solution against EDTA solution. A change of colour from winered to blue indicates end point.

Part 2: Determination of Total hardness. Pipette out 25 ml. of given hard water sample in a clean conical flask. Add 2 ml. of buffer solution and 3-4 drops of EBT indicator. Titrate this solution against EDTA solution until the colour changes from wine red to blue.. Note the titre Value, which corresponds to total hardness.

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Department of Applied Chemistry Part 3: Determination of Permanent Hardness.

Practical Manual

Pipette out 100ml of given hard water sample in 250 ml borosil conical flask, boil gently to reduce to 1/3rd of its volume. Filter it into 250 ml volumetric flask. Wash the funnel along with the filter paper, 3-4 times (about 10ml each washing) with distilled water and collect the washings in volumetric flask .Make up the volume using distilled water. Transfer the solution to 250 ml clean beaker. Now pipette out 25 ml of diluted hard water sample, add 2 ml of basic buffer solution and 3-4 drops of EBT indicator. Titrate with EDTA solution until the wine red colour changes into blue.This titre value (on multiplying by 2.5) corresponds to the permanent hardness.

Observation Table:

Part 1 : Standardization of EDTA Control reading: S.No Vol. of std. Hard water Vol.of EDTA solution ml

Constant Reading.

Part 2: Determination of Total Hardness of water.

Control reading: Vol. of given. S.No Hard water sample Vol.of EDTA solution

ml Constant Reading.

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Department of Applied Chemistry Part 3: Determination of Permanent Hardness: Control reading: Vol. of boiled S.No Hard water sample. Vol.of EDTA solution

Practical Manual

ml Constant Reading.

Calculations: For part 1: Standardization of EDTA Let 1.2 g of CaCO3 is dissolved in 1000 ml of water. Wt. of the CaCO3 Molarity of std. Hard water = -------- -------------------------------------Mole. wt. of CaCO3 X Vol. X 1000

=M( M1) Std Hard water M1 V1 = EDTA M2 V2 M1 V1 M 2 = -----------------V2 = ( molarity of EDTA) Part 2 : Determination of Total Hardness present in given water sample. EDTA M2V2 M3 = Water Sample M3V3 M2V2 = -----------------V3 = (molarity of hard water) Shri Ramdeobaba Kamla Nehru Engineering College, Nagpur 12

Department of Applied Chemistry Total Hardness Wt/Lit = M3 x Mole. Wt. of CaCO3 = = = ------------- g/lit. ------------ x 1000 mg/ lit. -- ppm. (Total Hardness.)

Practical Manual

Part 3 : Determination of Permanent Hardness present in given water sample. EDTA M2V2 M4 = Water Sample M4V4 M2V2 = -----------------V4 = (molarity of diluted hard water) Permanent Hardness Wt/Lit = M4 x Mole. Wt. of CaCO3 = = = ------------- g/lit. ------------ x 1000 mg/ lit. -- ppm.(Permanent Hardness)

Temporary Hardness = Total hardness Permanent hardness

Result:

The given water sample was found to contain Total hardness = Permanent hardness = Temporary hardness = ppm, ppm and ppm

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Department of Applied Chemistry

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EXPERIMENT NO. 3
AIM: To Estimate Copper in the given copper sulphate solution by Iodometry.

THEORY: The Iodometric method of volumetric analysis is based on oxidation reduction process (Redox) and involves interconversion of elemental Iodine into and Iodide ions and vice-versa asIodometry 2 I - -------------- ---------Iodimetry There are two types of Iodometric titrations a) Indirect Iodometric titrations (Iodometry) involves titrations of iodine liberated from potassium iodide (KI) in a chemical reaction. b) Direct Iodometric titrations (Iodimetry) involves titrations with Std. solution of Iodine.
PRINCIPLE: In this Experiment an oxidizing agent such as K2Cr2O7 or CuSO4 is treated in acid

I2 + 2e-

solution (dil. H2SO4) with an excess of iodide ion produced by KI. The oxidizing agent oxidizes the iodide ions into Iodine, which is then titrated with the std. solution of reducing agent such as sodium thiosulphate solution. Chemical Reactions: PART A: Standardization of Sodium thiosulphate solution.

1)

K2Cr2O7 + 6KI + 7H2SO4

3I2 + Cr2(SO4)3 + 4K2SO4 + 7H2O

In ionic form, the same reaction can be written as Cr2O72- + 6I- + 14H+ 3I2 + 2Cr3+ + 7H2O

2)

2 Na 2S2O3 + I2

2Na I + Na 2 S4 O6 Sodium tetrathionate

Sodium thiosulphate

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Department of Applied Chemistry In ionic form, the same reaction can be written as 2S2O32- + I2 2I- + S4O62-

Practical Manual

PART B: Estimation of copper ions

2CuSO4 + 4KI

Cu2I2 + I2 +2 K2SO4

In ionic form, the same reaction can be written as 2Cu2+ + 4 I2CuI2 Cu2I2 + I2

The amount of iodine thus generated depends upon the concentration of Cu2+ ions and the amount of I2 generated can be found out by titrating against sodium thiosulphate solution. . Since the solubility of Iodine in water is low, a considerable excess of KI must be used in iodometric determination of oxidizing agent. The iodine liberated by the reaction then dissolves by forming the complex K (I3) I-+ I2 (I3)-

KI + I2

K (I3)

OR

Formation of this compound (I3)- does not interferes with in the titration of iodine with thiosulphate because as free iodine is used with thiosulphate, the equilibrium between I2 and (I3)- is disturbed and more I2 is produced by the backward reaction. After addition of KI and /or acid the flask is kept in dark place for about 5 minutes as rate of the reaction between oxidizing agent and I- is too low.. Secondly, light accelerates side reaction 4I-+4H+ + O2
-

2I2 + 2H2O

In which I are oxidized to I2 by atmospheric oxygen and analytical results may go wrong. It is for this purpose therefore before adding KI to the acidic solution of the oxidizing agent, a pinch of Na2CO3 is added so as to generate a CO2 atmosphere which would prevent access of the O2 to the solution.

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Department of Applied Chemistry Indicator:

Practical Manual

Most commonly used indicator in iodometric titration is STARCH. It forms deep blue complex with iodine (but not with iodide) Starch is a polymer, consisting of two components Amylose and Amylopectine. The active fraction amylose is a polymer of the sugar D- glucose. It has a shape of coiled helix into which I2 combined with I- can fit, thus reacting slowly with thiosulphate. Due to this reason the starch solution must be added at the very end of the titration (when iodine conc. is very less). Starch solution is not very stable solution because various microorganisms are degrading it and one of the degradation products, glucose, is a reducing agent. Thus an old starch solution containing some glucose can cause an appreciable titration error. Hence always fresh starch solution is used. PROCEDURE: -

Part A: -Standardization of sodium thiosulphate solution. Pipette out 25ml. std. K2Cr2O7 solution in a conical flask. Add 10 ml.dil. sulphuric acid,

followed by a pinch of sodium bicarbonate /sodium carbonate and finally 10 ml KI (10%). Keep the flask covered for 5-6 minutes in dark. Appearance of dark brown color indicates the formation of I2. Now, titrate it against Na2S2O3 from burette until dark brown colour becomes faint brown. At this stage, add 2 ml. starch solution, colour of the solution becomes intense blue. Continue titration drop wise till blue color disappears. Note this point as an end point. Part B: -Estimation of Cu2+ ions. Pipette out 25 ml. given CuSO4 solution in a conical flask. Add few drops of dil. Na2CO3 solution until a faint permanent precipitate remains. Add acetic acid solution dropwise till the solution becomes clear. Now add 10 ml. KI (10%). Appearance of dark brown colour indicates formation of I2. Titrate the liberated iodine with Na2S2O3 solution from burette till brown colour of iodine fades, then add 2ml. of starch solution, and continue the addition of the Shri Ramdeobaba Kamla Nehru Engineering College, Nagpur 16

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Na2S2O3 solution until the blue color commences to fade. Then add about 5-6ml of ammonium thiocyanate solution into the flask due to which blue color become more intense. Continue the titration till blue color disappears (there is formation of flesh coloured ppt in the flask). Note this point as an end point.

Calculations:-

Given Normality of std. K2Cr2O7 is N1 Part A: -Standardization of Sodium thiosulphate solution.(Hypo.) Std. K2Cr2O7 N1V1 v/s = Hypo N2V2

N1x 25 N2

= N1x 25

N2 X V2

= ----------------V2 = X

Part B: -Estimation of Cu2+ions. Hypo N2V2 v/s = given CuSO4 N3V3 N2V2 -----------25 Y (Normality of CuSO4 solution.) = Normality x Eq. Wt. Of Cu2 + ions = = N3 X 63.546 Z g/l

N3 = N3 =

Wt./lt.of Of Cu 2 +

Result: The given solution of copper contains Z g/l of Cu2+ ions.

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Department of Applied Chemistry Precautions: 1) To suppress the volatility of Iodine, excess of KI is added.

Practical Manual

2) Flask is to be kept in dark to avoid photo oxidation of Iodide ions to Iodine. 3) Freshly prepared starch solution only can be used as an indicator.

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Experiment N0. 4
Aim: Estimation of chlorine in the given water sample. Reagents required 1. Std K2Cr2O7 Solution 2. KI solution (10%) 3. Dilute H2SO4 solution 4. NaHCO3 5. Sodium thiosulphate solution 6. Starch solution

Theory: Living organisms such as algae, fungi and bacteria are more abundant in surface drainage waters while in deep well waters, the bacterial count is often low .The growth of these organisms in water may have serious consequences .The slime surrounding these organisms causes them to adhere to the metal surfaces and the film of slime thus formed serves as a base to which suspended matter present in the water can adhere. This leads to a serious reduction in the heat transfer rates and tube blockages. The growth of marine organisms such as mussels may lead to serious reduction in the carrying capacity of pipelines and culverts. Thus measures to prevent the development of the living organisms are often necessary. Organism growth generally take place most readily in water at temperature range between 10 - 35 0C. Chlorine is widely used for disinfecting water to remove bacteria, fungus and other pathogenic microorganisms and for deodorization, as it is a powerful oxidizing agent and is cheaply available. Chlorination can be carried out by using bleaching powder or chlorine gas or chlorine dissolved in water in the form of concentrated solution or with chloramines.The sterilizing action of is supposed to be due to its reaction with water producing hypochlorus acid and nascent oxygen both of which have powerful germicidal properties.

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Department of Applied Chemistry Reactions: CaOCl2 + H2O Ca (OH) 2 + Cl2

Practical Manual

Cl2 + H2O HOCl Hypochlorus acid

HOCl + HCl

HCl + [O] nascent oxygen

Principle: The principle involved in the estimation of chlorine in water is that when a measured quantity of water is treated with excess of potassium iodide, the free chlorine present in the water oxidizes the corresponding amount of potassium iodide to Iodine. The liberated iodine is estimated by titrating against sodium thiosulphate solution.

Cl2 + 2KI I2 + 2Na2S2O3

----------

2KCl + I2 Na2S4O6 + 2NaI sodium tetra thionate

Sodium thiosulphate

Procedure:

Part A: - Standardization of Hypo solution Pipette out 25ml. std. K2Cr2O7 solution in a conical flask. Add 10 ml.dil. sulphuric acid,

followed by a pinch of sodium bicarbonate /sodium carbonate and finally 10 ml KI (10%). Keep the flask covered for 5-6 minutes in dark. Appearance of dark brown color indicates the formation of I2. Now, titrate it against Na2S2O3 from burette until dark brown colour becomes faint brown. At this stage, add 2 ml. starch solution, colour of the solution becomes intense blue. Continue titration drop wise till blue color disappears. Note this point as an end point.

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Department of Applied Chemistry Part B: - Determination of chlorine in the given water sample.

Practical Manual

Take 25-ml.given water sample in a conical flask. Now add 10 ml. KI (10%). Appearance of dark brown color indicates formation of I2. Titrate the liberated iodine with Na2S2O3 solution from burette till brown color of iodine fades, then add 2-ml. of starch solution, and continue the addition of the Thiosulphate solution until the blue color disappears completely. Note this point as an end point.

Calculation:-

Given Normality of std. K2Cr2O7 is N1 Part A: -Standardization of Sodium thiosulphate solution.(Hypo.) Std. K2Cr2O7 N1V1 N1x 25 v/s = Hypo N2V2 N2 X V2

= N1x 25

N2

= ----------------V2 = X

Part B: - Determination of chlorine in the given water sample. Hypo v/s given water sample

N2V2

N3V3 N2V2 -----------25

N3 = N3 =

Y (Normality of given water sample.)

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Department of Applied Chemistry Wt./lt. of Chlorine = = = N3 Z g/l

Practical Manual Normality x Eq. Wt. of Cl 2

X

35.5

Result: -

The water sample contains --------------g/l of chlorine.

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Department of Applied Chemistry

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EXPERIMENT NO. 5
Aim: - To estimate the amount of Ferrous, Ferric and total Iron present in the given solution.

Principle: The amount of ferrous ions present in the given solution containing ferrous and ferric salt is determined titrimetrically by titrating the solution with standard K2Cr2O7 solution. Then the Ferric ions are reduced to ferrous with a reducing agent such as SnCl2 and then the

total iron (present now in the ferrous state only) is titrated with standard potassium dichromate. 1) Cr2O72- + 6Fe2+ + 14H+ 2) 2Fe3+ + Sn 2+ 2Cr3+ + 6Fe3+ + 7H2O 2Fe 2+ + Sn 4+

In acid solution, when may be represented as: Cr2O7 2- + 14H + + 6e-

potassium dichromate oxidizes, it it itself is reduced which

2Cr3 +

+ 7H2O

From which it follows that the equivalent wt. of Potassium dichromate is one sixth of molecular weight i.e ; 294.22/6 = 49.03 g.

Internal indicators used for redox titrations (barring starch used in-iodometric titrations ) change colour when the oxidation potential of the titrated solution reaches a definite value. Such colour changes do not depend on the specific properties of the oxidation reduction or redox indicators. Such indicators include diphenylamine, neutral red, methylene blue, diphenylaminebenzene sulphonic acid, N- phenylanthranilic acid etc. Ferric salts are not oxidized either by dichromate or permanganate. They can be determined in solution only after reduction of Fe3+ to Fe2+ ions. This reduction can be done by

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reducing agents such as SnCl2. Ferric salt e.g. FeCl3 is reduced by the action of SnCl2 in presence of hydrochloric acid.

2FeCl3 + SnCl2

2FeCl2 + SnCl4

The excess SnCl2 must be removed completely, as K2Cr2O7 oxidizes it. This is done by adding mercuric chloride, which reacts with SnCl2 as follows:

SnCl2 + 2HgCl2 (Excess added)

SnCl4

Hg2Cl2

(silky white ppt)

Mecurous chloride (Hg2Cl2) is deposited in the form of silky white precipitate. The solution is directly titrated with K2Cr2O7. Following reaction takes place: -

Cl2 + K2Cr2O7 + 14HCl

6FeCl3 + 2KCl + 2CrCl3 + 7H2O

The following points must be taken into consideration in this analysis. The precipitated Hg2Cl2 can also oxidize by dichromate. However, if only a small excess of SnCl2 is used in the previous stage, the amount of HgCl2 precipitated is small. It reacts with the dichromate slowly and no appreciable error is introduced into the result. On the other hand, if a large excess of Hg2Cl2 is precipitated and, in particular, if it has a grey or dark colour as a result of further reduction to metallic mercury by the reaction as follows:

Hg2Cl2 + SnCl2

2Hg + SnCl4

Then it is oxidized so rapidly in the titration that the result is quite erroneous. It follows, therefore, that an important condition for accuracy in this method is the use of a very slight excess of SnCl2. Stannous chloride is added drop by drop until the reddish

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yellow/ yellow colour of FeCl3 has completely disappeared, after which one or two more drops are added.

PROCEDURE: Part-I: Determination of Ferrous ion Pipette out 25 ml. of the given ferrous ferric solution in a conical flask, add about 10 ml. of 4N sulphuric acid and 4-5 drops of N- Phenylanthranilic acid indicator. Titrate slowly with constant shaking of the flask against K2Cr2O7 solution. Appearance of a violet red or brickred colouration marks the end point. This titre value corresponds to the ferrous ions present in the solution. Determination of Total Iron (Fe3+ & Fe2+)

Part-II:

Pipette out 25 ml. of the given ferrous ferric solution in a conical flask. Add about 10 ml. of concentrated HCl. Its colour changes colourless to yellow. Heat the contents of the flask to boiling and to this hot solution add SnCl2 dropwise with continuous stirring till the solution becomes colourless. Do not add excess of SnCl2 . Cool the flask rapidly under tap water. Add 5 ml of mercuric chloride, a light silky white precipitate of mercurous chloride is formed. (if black ppt occurs it indicates that too much SnCl2 was added. In this case discard it. To the white ppt containing solution add 4-5 drops of N- Phenylanthranilic acid indicator. Titrate slowly with constant shaking of the flask against titration faint green colour develops which changes to Std K2Cr2O7 solution. At the end of violet-red or brick-red colour. This

marks the end point. This titre value corresponds to the total iron present in the solution. Difference between these gives the iron present in ferric state.

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Department of Applied Chemistry CALCULATIONS: Part-I: Determination of Ferrous ion . Std K2Cr2O7 Vs Fe2+ / Fe3+ mixture

Practical Manual

N1V1

N2V2

N1V1 N2 = ---------------V2

Where,

N1 and V1 are the normality and volume respectively of the

K2Cr2O7 solution and V2 is the volume of the Fe2 + / Fe3+ mixture used during part I. Wt./ lit.of Fe2+ =

N2

55.85

x g.

(Eq. Wt. Of Fe) Determination of Total Iron ( Fe3+ & Fe2+ ) K2Cr2O7 vs. Fe2+ (after reduction of Fe3+ by SnCl2) N1V1 = N3V3

Part-II:

N3

N1V1 --------------V3

Where,

N1 and

V1

are the normality and volume of the Std. dichromate

solution and V3 the volume of the Iron solution used during Part II. N3 x 55.85 = Wt. / lit. of total iron = Y g Wt/lit of Fe3+
2+

= (y-x) g = z g.

Result: The amount of Fe and Fe3+ present in the sample are: ------.

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Practical Manual

EXPERIMENT NO. 06
Aim: Determination of viscosity of a Lubricating Oils at different Temperatures by Red -Wood Viscometer.

Apparatus: Redwood viscometer (1 or 2), thermometer, energy regulator, etc.

Theory and General Discussion: Viscosity is one of the most important properties of liquid. Viscosity is a measure of the internal resistance to the motion of a liquid and is mainly due to the forces of cohesion between the liquid molecules. Viscosity of the liquid may be measured in several ways, one of which is determining time required for a definite amount of the liquid to flow through a capillary. Such method includes the use of Saybolt, Engler and Redwood Viscometers. Viscosity may be expressed as dynamic (or absolute) viscosity, kinematic viscosity or the viscosity coined after the name of the apparatus used for its determination. Dynamic or Absolute Viscosity: Dynamic or absolute viscosity (often denoted by ) is the tangential force per unit area required to maintain unit velocity gradient between two parallel planes, unit distance apart in the fluid. It can be also be defined as the ratio of shearing stress to the rate of shearing strain. If F is the force required to keep moving an particle of surface area A in contact with the fluid, separated from stationary surface by a thickness D, and moving with velocity V, then Shearing stress = Force acting on the surface area A and rate of shearing strain = V/D Absolute Viscosity ( ) = Shearing stress/ rate of shearing strain.
F / A FD = V /D VA = F A

(1) (2)

(3)

The numerical value of depends upon the unit used in equation (3). In metric system the unit is poise (F = 1 dyne, A = 1 cm. and V = km/sec.). A smaller unit, the centipoise is more

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often used. Poise is equal in one dyne.sec/cm2 (Dimensions of absolute viscosity are ML 1T-1). Absolute viscosity is also referred to as coefficient of viscosity.

Kinematic Viscosity: -

The ratio of absolute viscosity to density for any liquid is known as absolute kinematics viscosity. It is donated by . Its units is stoke. A smaller unit, centistokes (1/100 often used.
th

of stoke) is

=
Where,

(4)

= Absolute kinematic viscosity

= absolute dynamic viscosity

= density of liquid. Dimension of is L2 T1

Since the rate, at which a liquid will flow through an apparatus increases as the viscosity of the liquid decreases the rate of flow through an orifice or short tube may be used as a means for measuring viscosity. This is the principle involved in the Redwood viscometer, which is used in UK and India whereas Saybolts Viscometer is used in U.S.A. Englers Viscometer is used in Europe. In these viscometers a fixed volume of the liquid is allowed to flow (in case of Redwood it is 50 ml, Engler-200 ml and Saybolt 60 ml.) through a capillary tube of specified dimension under given set of conditions and the time of flow is measured at a particular temperature. The result is usually expressed in terms of the time in seconds taken by fixed volume of the liquid to flow through the standard orifice of the particular apparatus used. e.g.: Viscosity of oil is 250 sec using Redwood ( no. 1 or 2) at 270C. This Viscosity so determined is also called as Relative Viscosity.

Absolute and kinematic Viscosities can also be determined from the relative Viscosity (i.e. Redwood values) from the equations:

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Practical Manual (5)

= Ct
(for liquid whose kinematic viscosity is more than 10 centistokes)

= Ct / t

(6)

(for liquid whose Kinematics Viscosities less than or equal to 10 centistokes) Where,

= kinematic viscosity in centistokes

t = time of flow in seconds

C = viscometer constant = coefficient of kinetic energy which may be determined experimentally or eliminated by choosing long flow-times

Test Viscometer may be calibrated by solutions of known viscosity. The primary standard used is freshly distilled water, whose kinematic viscosity is 1.0008 centistokes. Other standards usually employed are40% sucrose solution 60% sucrose solution.

= 4.390 cs at 25 0C
= 33.66 cs. at 25 0C

For Redwood viscometer No.1, the values for the constants are as below:

Time of flow, t 40 to 85 seconds 85 to 2000 seconds

190 65

C 0.264 0.247

For Redwood viscometer No.2, the values for the constants are =1120, C= 2.720

Redwood viscometer No. 2 is used for very viscous liquids which require 2000 or more seconds for specified volume of the liquid to flow.

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Department of Applied Chemistry Brief mechanism of lubricants:

Practical Manual

The formation of a fluid film of a lubricant between the moving friction surface and the generation of the frictional heat under the particular condition of load, bearing speed and lubricant supply is mainly depends upon the viscosity of the lubricant and to some extent on its oiliness. If the viscosity of the oil is too low, the fluid lubricant film cannot be maintained between the moving surfaces as a result of which excessive wear may take place. On the other hand, if the viscosity of the oil is too high, excessive friction due to the shearing of oil itself would result. Hence in hydrodynamic lubrication, the lubricant should posses the proper viscosity. So, it is of vital importance to have knowledge of the viscosity of the lubricating oil.

Procedure: 1) 2) Level the instrument with the help of spirit level. Put the valve rod at its position (i.e. in the concavity at the bottom of the cup) to close the opening of orifice. 3) 4) Keep clean dry Kohlrauschs flask centrally below the jet. The test sample is poured into the oil cup and adjust the level of oil, with that of the pointer. 5) Cover the oil cup with the lid and insert thermocouple / thermometer of desired range into the oil cup from the thermometer bracket. Care should be taken that it dose not touch the bottom of the cup. 6) Fill up the water bath with water and adjust the level of water with that of the pointer in the oil cup. Let the oil in the cup to attain the room temperature. 7) Lift up the value rod and suspend it from the thermometer bracket and start the stop watch simultaneously. 8) Receiving flask is so located that oil strikes the flared mouth and does not drop directly into the opening, which would cause foaming. 9) When the level of the oil reaches 50 ml. mark in the neck of the flask, stop the stop-watch. 10) At the same time close the passage of the orifice by keeping the valve rod at its original position to prevent any overflow of oil. 11) The time elapsed in seconds is the relative viscosity of oil at room temperature.

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Practical Manual

Again, pour oil into the cup and adjust oil level a little lower than the pointer. Check the oil level and draw or add a little oil so as to be exactly at the pointer. Switch on the water bath adjust the knob of the so as to heat the water and raise the temperature of the oil to say 85 oC or 80 oC.

15)

When the temperature of sample has become steady at the desired value lift the valve rod and suspend it from the thermometer bracket and start the stopwatch simultaneously.

16)

When the level of the oil touches the 50 ml. mark on the neck of the flask stop the watch. The time elapsed in seconds in the relative viscosity of oil at elevated temperature. (85 oC or 80 oC as the case may be)

17)

Now take out some hot water from the water bath and add equal amount of cold water to bring the temperature of the bath.

20) 21) 22)

Pour oil into the cup and adjust oil level as described earlier. Stir the contents of the bath and cup regularly. When the temperature of sample has become steady at the desired temperature 75
o

C or 70 oC. Find out the relative viscosity of test sample at this temperature as

described earlier. 23) Repeat the procedure to find out relative viscosities of oil at 65 0C, 55 0C, 45 0C, respectively. 24) 25) Record all the results in the tabular form. Plot graph corelatively (a) Viscosity and temperature, (b) Log of viscosity and temperature and (c) Kinematic viscosity and temperature . (d) Log of Kinematic viscosity and temperature, (e) Find rate of change of viscosity with respect to temperature.

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Department of Applied Chemistry Observation table: Redwood viscometer no.: c = = Sr. No. Temperature (T) in 0C Time in second Kinematic (Relative Viscosity) ( r ) 1 2 3 4 5 6 7 8 Room Temp.: Viscosity ( ) in centistroke

Practical Manual

Log ( r ) Log ( )

Calculation:

Plot the following graphs

1. Relative viscosity ( r ) against the temperature of sample (T) 2. Log of relative viscosity ( r ) against the temperature of sample (T) 3. Kinematic viscosity ( ) against the temperature of sample (T) 4. Log of kinematic viscosity ( ) against the temperature of sample (T) and also determine the slope of the graph 1

Result :-The rate of change of relative viscosity with respect to temperature was found to be equal to ------------

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Practical Manual

EXPERIMENT NO. 07
Aim: Determination of Flash Point of given sample by using flash point apparatus.

Theory:. The Flash Point of sample may be defined as the minimum temperature to which it must be heated to give off sufficient vapors to ignite momentarily when a flame of standard dimensions is brought near the surface of the sample for a prescribed rate in an apparatus of specified dimensions. This is detected by the appearance of momentary flash upon the application of standard flame over the surface of sample. The Flash Point is defined as closed cup or open cup flash point accordingly as the apparatus for the determination of flash point of sample is provided with a cover the sample cup or not. This parameter is not related to the temperatures of the ignition source or of the burning liquid, which are much higher. The mechanism of the appearance of the flash can be explained in the following manner. Every flammable liquid has a vapor pressure, which is a function of that liquid's temperature. As the temperature increases, the vapor pressure increases. As the vapor pressure increases, the concentration of evaporated flammable liquid in the air increases. Hence, temperature determines the concentration of evaporated flammable liquid in the air. Each flammable liquid requires a different concentration of its vapor in air to sustain combustion. The flash point of a flammable liquid is the lowest temperature at which there can be enough flammable vapour to ignite, when an ignition source i.e. flame of suitable dimension is applied. Importance of flash point from view of lubricants: A good lubricating oil should not volatilize under the working temperatures. Even if some volatilization takes place, the vapors formed should not form inflammable mixture with air under the condition of lubrication. From this point of view, the flash point of a lubricating oil are of vital importance. Lubricating oil selected for a job should have a flash point which is reasonably above its working temperature. This ensures the safety against the fire hazards during the storage, transport and use of the lubricating oil. This test is immense importance for illuminating and Lubricating Oils. This helps in detecting the highly volatile constituents of the oils. If they are highly volatile at ordinary temperature, the issuing vapors may cause fire hazards. So to ensure

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Practical Manual

safety, certain minimum temperatures are laid down for fuels and Lubricating Oils below which they should not give off adequate vapors to make them burn.

Outline of the Method: The sample is placed in the cup of apparatus and heated at a slow uniform rate about 2 o C . A small test flame is directed into the cup at regular intervals, and the lowest temperature at which application of the test flame causes the vapor to ignite momentary, with a distinct flash inside the cup, is recorded as Abels Flash Point. Description of the apparatus: The Abels apparatus consists of the following parts: a. SAMPLE CUP: This is a cylindrical vessel with a lid. Within the cup, near the top; there

is a sample level mark. b. COVER: The cup is provided with a close fitting cover. The cover is provided with a

thermometer socket, to support an oil test lamp, a movable metal bead. The top of the cover has three rectangular holes which are covered on uncovered by moving the slide which has two perforations to allow air to enter the sample up and bring contact between vapours of the sample and the test-lamp when in open position. A metal bead, the dimension (4mm) of which represents the size of test flame, is mounted in the cover. The apparatus is also provided with a stirrer. (C) HEATING VESSEL: - The heating vessel consists of copper vessel and placed

coaxially, which serves as a water jacket. When the sample cup is placed into the hole at the top of the vessel, it fits into it and leaves an air gap between itself and the outer copper water vessel. The water can be heated electrically or with a burner or spirit lamp. Thermometer is provided with the apparatus for the measuring the temperature of the sample. Procedure: Fill the given sample in such a way that the sample level is exactly upto the mark in the cup. Fix the cup into the apparatus and cover with lid. Insert the thermometer in the thermometer holder given in the cup in such a manner that it will not directly touch the lower bottom of the cup and the paddle stirrer inside the cup. Fill the water bath with the cold water. Close the sliding shutter and light the standard flame. Adjust the size of flame (4 mm diameter) with respect to the metal beed. Stir the oil using paddle stirrer. Introduce the flame by opening

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Practical Manual

the shutters and check the appearance of the flash. Now heat the apparatus and set the rate of temperature increase at the rate of 1 to 2 o C per minute. Check the flash point of given sample at the interval of 3 o C rise in the temperature. Discontinue the stirring the sample during the introduction of the test flame. On observing a flash, stop the heating process and allow the temperature to decrease. Check the occurrence of a flash at every 1 o C drop in temperature. Record the lowest temperature at which the flash is observed as the flash point of the sample. Observation: Table 1 ============================================ S. No. Increasing Inference Temperature (0C) (No flash or flash observed) ============================================ 1. Room temp 2. 3. 4. 5.

=============================================== Table 2 ================================================= S. No. Decreasing Inference Temperature (0C) (Flash observed or no flash) ================================================= 1. 2. 3. 4. 5. ================================================ Result: The Flash Point of given sample determined by Ables Flash Point apparatus is found to be ------0C

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Practical Manual

EXPERIMENT NO. 08
Aim: - Determination of Flash Point of a sample by using Pensky Martins closed cup apparatus.

Description of the Apparatus: A Pensky Martins apparatus consists of the following parts:

SAMPLE CUP: Sample Cup is a cylindrical vessel, made of brass with a filling mark grooved inside near the top. It is provided with a lid.

LID: The lid is equipped with the following parts:

i)

Stirrer: The stirring device consists of a vertical steel shaft mounted in the center of the

cup and carrying two-bladed brass propellers.

ii)

Cover: It has four openings: one for thermometer and the rest for the oxygen entry and

exposure of vapors to test flame.

iii)

Shutter: The lid is equipped with a brass shutter operating on the plane of the upper

surface of the cover proper. The shutter is so shaped and mounted on the lid that when in one position, the holes are completely closed and when in the other, these orifices are completely opened.

iv) The Flame Exposure Device: The lid is equipped with a lamp with such a mechanism that its flame operates simultaneously with the shutter. When the shutter is in the open position, the tip is lowered down in the center of the central orifice.

v)

Heater: The cup is heated by means burner or it is electrically heated. The air bath has

cylindrical interior about four cm. Deep and can be heated by a direct flame or an electric resistance element. The top-plate is also made of metal and mounted with an air gap between it and the air bath.

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Practical Manual

Procedure: The cup and its accessories are well cleaned and dried before the test is started. Now the cup is filled with the sample to be tested up to the level indicated by the filling mark and covered with the lid. The cover incorporating the stirring device, the thermometer and flame exposure device is fixed on the top. The cup is now set in the apparatus properly and the thermometer inserted. The test flame is lighted and adjusted until it is the size of a bead (approximately 4mm in diameter). The apparatus is heated so that the heating rate is maintained, with the help of a rheostat, at about 5 0C per minute and stirring rate at one-two rps. Once the heating is started, the test flame is applied after each 2 0C rise of temperature nearer to the sample in the cup by opening the shutter and check the appearance of the flash. On observing a flash, stop the heating process and allow the temperature to decrease. Check the occurrence of a flash at every 1 o C drop in temperature. Record the lowest

temperature at which the flash is observed as the flash point of the sample.

Observation: Table 1

Sr. No.

Increasing Temperature in o C

Observation (No flash or flash

observed) 1 2 3 4 5 6 7 8

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Table 2

Practical Manual

S. No.

Decreasing in C
o

Temperature Observation (Flash observed or No flash)

1 2 3 4 5 6

RESULT: The Flash Point of given sample determined by Pensky Martens Flash Point apparatus is found to be ---------0C

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Practical Manual

EXPERIMENT NO. 09
Aim: Determination of Flash Point and fire point of the given sample by Clevelands open cup apparatus. Definitions: I) Flash Point: Defined earlier.

II) Fire point: It is defined as the minimum temperature at which the oil gives off sufficient vapor which causes it to burn for a period of five seconds or more when a test flame is passed over surface of the oil.

Description of Apparatus: The apparatus consists of a test cup made of without any lid and is equipped with a handle. The cup is supported by a metal plate known as heating plate. The cup may be heated by an electric heater mounted below the cup in the apparatus itself.

The metal plate has an extension for mounting the test flame and the thermometer support. The test flame is mounted in such a manner as to permit automatic duplication of the sweep of the test flame over the sample cup. The size of the flame can be adjusted with respect to the dimension of metal beed. (approximately 4 mm)

Procedure: The apparatus is thoroughly cleaned and the thermometer is suspended in such a way so that the bottom of the thermometer bulb just above the bottom of sample cup. The cup is now filled with sample up to the filling mark grooved on the inner side of the The test flame is adjusted to have a flame diameter approximately to the dimension of metal beed. Now move the test flame over the sample cup and check the appearance of flash over the sample inside the cup.

If no flash observed, increase the temperature of the sample taken and take a flame over the cup after every 2 0C increase. On observing a flash, stop the heating process and allow the

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Practical Manual

temperature to decrease. Check the occurrence of a flash at every 1 o C drop in temperature. Record the lowest temperature at which the flash is observed as the flash point of the sample. Observation: Table 1 Sr. No. 1 2 3 4 5 6 7 8 Increasing Temperature in o C Observation (No flash observed) or flash

Table 2 S. No. Decreasing in o C Temperature Observation (Flash observed or No flash)

1 2 3 4 5 6

Result: Flash Point of given sample determined by Clevelands apparatus is found to be ----- ----0C.

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Practical Manual

EXPERIMENT NO. 10
Aim : Determination of Chemical Oxygen Demand in a waste water sample.

Apparatus: Reflux apparatus, consisting of a 250 ml.-flat bottomed Borosil flask with ground glass joint and a condenser.

Regents required:

1. Standard 0.25 N K2Cr2O7 solution 2. Sulfuric acid-silver sulphate reagent: 3. Standard 0.1 N Fe (NH 4) 2SO4. 7H2O solution: 4. Ferroin indicator 5. HgSO4

+2

N Fe N . SO -4-2

Figure: Structure of ferroin indicator Theory: In Environmental Chemistry, the Chemical Oxygen Demand (COD) test is commonly

used to measure the amount of organic compounds that is susceptible to oxidation by a strong oxidant present in water. Any organic matter such as hydrocarons when brought in contact with oxygen is oxidised to get CO2 and H2O. If the organic matter contains hydrogen, nitrogen, sulphur, etc. in addition to carbon, then the chemical oxidation leads to formation of CO2, H2O, NO2, SO2 and etc. To get thos oxidation, oxygen is required and demanded by this organic

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Practical Manual

material. The possibility of meeting such demand is through dissolved oxygen in the water. Thus dissolved oxygen in water gets depleted and survival of the bio-organisms in such water is difficult and sometimes impossible. It is therefore, essential to check COD of effluent water before letting it out from industr. It is expressed in milligrams per liter (mg/L), which indicates the mass of oxygen consumed per liter of solution. Older references may express the units as parts per million (ppm). The basis for the COD test is that nearly all organic compounds can be fully oxidized to carbon dioxide with a strong oxidizing agent under acidic conditions. The amount of oxygen required to oxidize an organic compound to carbon dioxide, ammonia, and water is given by:

This expression does not include the oxygen demand caused by the oxidation of ammonia into nitrate. The process of ammonia being converted into nitrate is referred to as nitrification. The following is the correct equation for the oxidation of ammonia into nitrate.

The second equation should be applied after the first one to include oxidation due to nitrification if the oxygen demand from nitrification must be known. Dichromate does not oxidize ammonia into nitrate, so this nitrification can be safely ignored in the standard chemical oxygen demand test. Using potassium dichromate Potassium dichromate is a strong oxidizing agent under acidic conditions. (Acidity is usually achieved by the addition of sulfuric acid.) The reaction of potassium dichromate with organic compounds is given by:

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Practical Manual

where d = 2n/3 + a/6 - b/3 - c/2. Most commonly, a 0.25 N solution of potassium dichromate is used for COD determination, although for samples with COD below 50 mg/L, a lower concentration of potassium dichromate is preferred. In the process of oxidizing the organic substances found in the water sample, potassium dichromate is reduced (since in all redox reactions, one reagent is oxidized and the other is reduced), forming Cr3+. The amount of Cr3+ is determined after oxidization is complete, and is used as an indirect measure of the organic contents of the water sample. Importance of Blank Titration Because COD measures the oxygen demand of organic compounds in a sample of water, it is important that no outside organic material be accidentally added to the sample to be measured. To control for this, a so-called blank sample is required in the determination of COD (and BOD, for that matter). A blank sample is created by adding all reagents (e.g. acid and oxidizing agent) to a volume of distilled water. COD is measured for both the water and blank samples, and the two are compared. The oxygen demand in the blank sample is subtracted from the COD for the original sample to ensure a true measurement of organic matter. Interference due to Chlorides in waste water Some samples of water contain high levels of oxidizable inorganic materials which may interfere with the determination of COD. Because of its high concentration in most wastewater, chloride is often the most serious source of interference. Its reaction with potassium dichromate follows the equation:

Prior to the addition of other reagents, mercuric sulfate can be added to the sample to eliminate chloride interference.

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Department of Applied Chemistry

Procedure: Part I

Practical Manual

Determination of COD value of the given waste water sample

Pipette out 10 ml of the wastewater sample in a reflux flask, dilute the sample by 20 ml with distilled water. Mix well and add 10 ml.of 0.25 N K2Cr2O7 solutions. Drop some pumice stones and slowly add 30 ml. of H2SO4AgSO4 reagent while continuously swirling the flask. If the colour changes to green, add more K2Cr2O7 and or alternatively discard the solution and take a fresh sample with lesser aliquot.. Mix the contents of the flask thoroughly. Connect the flask to the condenser and slowly heat flask. Reflux for at least 2 hours. Cool and wash down the condenser with distilled water such that the washings fall in to the flask. Add few drops of Ferro in indicator and titrate the content of the flask (un reacted K2Cr2O7) with the 0.1 N FAS solution. Near the end point the yellow colour of the solution gradually fades up to bluish green, continue the titration till bluish green colour changes to wine red color.

Part-II

Blank Titration Repeat the above procedure using 10 ml of the distilled water instead of the

Waste water sample for about half hour.

Part-III

Standardization of the FAS solution

Pipette out 10 ml of the FAS solution in a conical flask add few drops of the Ferroin indicator and titrate with the standard K2Cr2O7 solution till solution changes color from yellow to wine red colour.

Calculation: Part A] Standardization of FAS solution:

Std. K2Cr2O7 = FAS solution

N1V1

=
N2 =

N2V2
N1V1 V2

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Department of Applied Chemistry

Part B] Determination of COD of given water sample:

Practical Manual

The COD value of the sample is calculated as follows:

COD in mg/l =

(V4 -V3 ) N 2 8 1000 V

Where, V4= Volume of the FAS run down in the blank Experiment. V3 = Volume of the FAS run down in the test Experiment. N2 = Normality of FAS solution V = Volume of the test sample taken.

Result:

The Chemical oxygen demand of the given waste water sample was found to be equal to __________ppm.

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Practical Manual

Experiment No. 11
Aim: - To determine Acid Value or Neutralization number of given oil.

Introduction: The Acid Value of an oil is defined as the number of milligrams of potassium hydroxide required to neutralize the free acid present in 1 gram of the oil.

The presence of mineral acids in oil is so rare that it is almost unnecessary to look for it, unless the oil is refined in a faulty manner. Free organic acids or acidic bodies are always found in Oil, whether they be pure mineral oils or compounded oils with fatty oils. In unused refined petroleum oils, the quantity is invariably negligible.

In good oils, the Acid Value should be very low (<0.1). Increase in Acid Value should be taken as an indicator of oxidation of the oil, which may lead to gum and sludge formation besides corrosion. The Acid Value of fatty oils may vary from 0.2 to 50 and it shows the extent of hydrolysis of glycerol ester of the oil.

Regents required: (1) KOH solution (2) Neutral ethyl alcohol

(3) Phenolphthalein indicator.

Procedure: Part-I: Standardization of KOH Solution

Take 10ml of oxalic acid solution. Add few drops of phenolphthalein indicator. Titrate this with KOH solution from burette till there is a colour change. Note the end point as V2 .

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Department of Applied Chemistry

Part-II: - Determination of Acid value of Solution

Practical Manual

Weight out accurately about 5 g. of the oil under test into a 250 ml conical flask and add 50 ml of neutral alcohol. Heat the flask over a water bath for about 30 minutes. Cool the flask and the contents to room temperature and add a few drops of phenolphthalein indicator. Titrate with the standard N/10 KOH solution until a faint permanent pink color appears at the end point as V2.

Part-III: - Blank titration

Repeat the same procedure without taking lubricating oil.

Reaction: C17H35COOH+KOH ---------------- > C17H35COOK+H2O

Calculations:

Part-I: Standardization of KOH Solution Std Oxalic acid Vs KOH

N1V1

N2V2

N1V1 Normality of KOH i e; N2 = ---------------V2

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Department of Applied Chemistry

Part-II: - Determination of Acid value of Solution

Practical Manual

Normality of KOH x V2 x eq. wt. of KOH

Acid value =

--------------------------------------------------------Weight of the oil taken in g

Result: The Acid Value of the given oil is found to be_________.

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Practical Manual

Experiment No.12
Aim: - Determination of saponification Value of Oil.

Introduction: The saponification value of oil is the number of milligrams of potassium hydroxide required to saponify one gram of the oil. The vegetables or animal oils are esters of fatty acids and glycerol. They react with KOH to form the potassium salts of fatty acids. The saponification value of oil is determined by refluxing a known quantity of the sample with a known excess of standard KOH solution and determining the alkali consumed by titrating the unreacted alkali.

Reactions:

CH2OOCC17H35 | CHOOCC17H35 + 3KOH -------| CH2OOC17H35

CH2OH | CHOH + | 3C17H35COOK

CH2OH Fat Stearic acid glycerol potassium steareate

Reagents required (1) N/2 std Na2CO3 solution (2) alcoholic KOH solution (3) HCl solution

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Procedure: Part-I: Standardization of HCl solution

Practical Manual

Pipette out 10 ml of std. borax solution in a conical flask. Add phenolphthelin as an indicator. Titrate it with HCl solution till pink colour turns to colourless.

Part-II: - Saponification Value of oil

Weight out accurately about 5 g. of the oil into a 250 ml conical flask and add 50ml of N/2 alcoholic KOH solution to the flask. Reflux the contents over a water bath for

about 1.30 hr using water condenser. Wash the inner wall of the condenser with a small amount of distilled water and collect the washing into the same conical flask. Remove the flask from the water bath cool the flask and the contents to room temperature and add a few drops of phenolphthalein indicator. Titrate with the standardised N/2 HCl solution until solution becomes colourless. Note the end point as V2

Part-III: - Blank titration Perform the blank experiment by repeating the entire procedure similarly but without using the oil and titrate with the same standardized N/2 HCl as described above. Note the end point as V2 .

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Calculation: Part-I: Standardization of HCl solution

Practical Manual

Standard Borax solution N1V1 =

Vs

HCl

N2V2 N1V1

Normality of HCl i e;

N2

---------------V2

Part-II: - Determination of Saponification value

Actual volume of KOH Consumed

A] Actual volume of KOH required can be found by: HCl required for the titration of oil and alc. KOH is refluxed is------- V2

HCl required for the titration of only alc. KOH is (blank) ----------------V2

HCl used corresponding to used KOH is = (V2- V2) ml = V ml.

B] Calculation of normality of KOH: KOH solution Vs HCl solution NKOH X VKOH = NHCl X VHcl NHCl X VHcl NKOH = -----------------------------------VKOH C] Calculation of volume of HCl:
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Department of Applied Chemistry

Practical Manual

HCl Vs used KOH

N2 x V = N3 x V3 (?) V3 = N2 x V / N3 V3 = ---------ml.

V3 ml of KOH is used for saponification for x g of oil Say Normality of KOH =----- N Wt / litre = N KOH x 56 =z g

1000 ml of KOH = z g of V3 ml of KOH = z x V3 --------1000 = b g of KOH b Normality per gram of oil is = x b = ---- x 103 mg x
Result: Therefore the Saponification value of the given oil is found to be_________. found to be_________.

--- g

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