UNIT 1 PROBLEM SHEET 1 I. Units and dimensions i) 16.4 Btu / hr. ft.

O F ii) 10 Cal/ (g mol) K iii) 200 Ib / hr.ft2 iv) 400 in3/ day v) 100 Btu / Ib O F

to to to to to

W/m. K J/ (k mol) K kg / s. m2 cm3/min. J/ kg. K

II. The mole unit, mole fraction (or percent) and mass fraction (or percent), analyses of a Mixture, concentrations, basis of calculations, calculation of density. 1. Partial pressure of various components present in the sewage gas sample from a municipal sewage plant is given below: methane: 1.76 atm; carbon dioxide: 0.6 atm; ammonia: 0.04 atm (a) Calculate i) Composition in partial pressure% ii) Composition in mole% iii) Composition in volume% iv) Composition in weight% v) Average molecular weight (b) Calculate the density of the gas mixture at 30C and 2 atm pressure 2. Analysis of a sewage gas sample from municipal sewage plant is given below on partial pressure percent: methane: 66%; carbon dioxide: 28%; ammonia: 6% (a) Calculate i) Composition in volume% ii) Composition in mole% iii) Composition in weight% iv) Average molecular weight (b) Calculate the density of the gas mixture at 30C and 2 atm pressure. 3. Natural gas has the following components: CH4 : 8 m3; C2H6 : 1.2 m3 and N2 : 0.8 m3. (a) Calculate i) Composition in volume% ii) Composition in partial pressure% mole% iv) Composition in weight% v) Average molecular weight (b) Calculate the density of the gas mixture at 50C and 2 atm pressure. 4. Natural gas has the following composition by volume percent. CH4 : 83.5%; C2H6 : 12.5% and rest nitrogen. (a) Calculate i) Composition in partial pressure% ii) Composition in mole% iv) Average molecular weight (b) Calculate the density of the gas mixture at S.T.P. 5. The various components of a gas mixture are:

iii) Composition in

iii) Composition in weight%

N2 : 3.5 kmol; O2 : 0.9 kmol; H2O : 0.1 kmol and NH3 : 0.5 kmol . (a) Calculate i) Composition in mole% ii) Composition in partial pressure% iii) Composition in volume % iv) Composition in weight% v) Average molecular weight (b) Calculate the density of the gas mixture at 1 atm and 35 C. 6. The composition of a gas mixture in mole percent: N2 : 70.5%; O2 : 18.8%; H2O : 1.2% and NH3 : 9.5% . (a) Calculate i) Composition in volume% ii) Composition in partial pressure% iv) Average molecular weight (b) Calculate the density of the gas mixture at 1 atm and 65 C. 7. The various components of a product gas from a reaction are: chlorine : 62 kg , bromine : 25 kg and oxygen : 13 kg . (a) Calculate i) Composition in weight% ii) Composition in mole% iv) Composition in partial pressure% v) Average molecular weight (b) Calculate the density of the gas mixture at S.T.P. 8. A product gas from a reaction has the composition by weight%: chlorine : 67% , bromine : 28% and oxygen : 5% . (a) Calculate i) Composition in mole% ii) Composition in partial pressure% iv) Average molecular weight (b) Calculate the density of the gas mixture at 1 atm and 25 C.

iii) Composition in weight%

iii) Composition in volume%

iii) Composition in volume%

9. The analysis by weight percent of magnesite ore is: MgCO3 : 81%; SiO2 : 14%; and H2O : 5% . Calculate i) Composition in mole% ii) Average molecular weight 10. In the following table, various aqueous solutions are listed. The density of aqueous solution at 20 oC and its composition are listed. The density of the water at 20 oC is 0.998 gm/cc. Calculate the composition (other than the composition given as data) expressed in the following ways: (a) Composition in weight% (b) Composition in mole% (c) Composition in volume% (d) molarity (e) molality (f) normality (g) ppm Solute HCl H2SO4 NaCl LiCl KCl NaCl Composition of solution Weight % of HCl = 30 Mole % of H2SO4 = 36.8 Volume % of H2O = 20% Molality = 10.13 Normality = 2.70 ppm = 230 Valence 1 2 1 1 1 1 Density of solution at 20 C, g/cc 1.149 1.681 1.148 1.179 1.118 0.998

III. Predicting P-V-T properties of gases using the following equations of state: Ideal gas law, Van der Waals equation, Redlich-Kwong equation, calculation of density 1. What is the pressure, generated when 1 mol of methane gas is stored in a volume of 0.6095 m 3, at 50 C using Ideal gas law? Calculate the density of the gas at the given conditions and also at S.T.P & N.T.P. 2. Calculate the volume, using Ideal gas law, occupied by 14 kg of nitrogen gas at a pressure of 720 mm Hg and 20 C. Calculate the density of the gas at the given conditions and also at S.T.P & N.T.P. 3. A cylinder, of volume 0.150 m3, is filled with 22.7 kg of propane gas (C3H8). The pressure gauge shows the reading as 479 kPa. Calculate the temperature of the gas using Ideal gas law. Calculate the density of the gas at the given conditions and also at S.T.P & N.T.P. 4. Calculate the weight of 100 m3 (725 mm Hg and 25 C) of hydrogen gas using Ideal gas law. Calculate the density of the gas at the given conditions and also at S.T.P & N.T.P. 5. 1 kmol of C2H6 is stored at a temperature of 50C and at a pressure of 600 atm. Calculate the volume based on i) Van der Waals equation and ii)Redlich-Kwong equation. Compare them with the volume calculated by the Ideal gas law. Data: Pc = 45.8 atm. and Tc = 9 K for ethane.

FORMULAS Ideal gas Law PV = P = V = n = R = = T n Weight Density Density = = nRT Pressure, atm Volume, m3 Number of moles, kmoles ideal gas constant J Kcal atm m 3 0.0821 =8.315 =1.987 mol K kmole K kmole K Temperature, K Weight /Molecular weight Weight, kg Molecular weight, kg/kmole number of moles x molecular weight Mass/Volume, kg/m3 molal density x molecular weight (n/V) x Molecular weight Volume/number of moles,m3/kmole V/n Standard temperature and pressure (0C, 1 atm)

= = = = Molal volume = v = S.T.P =

N.T.P = Normal temperature and pressure (25C, 1 atm) Molarity = number of gmoles of solute/liter of solution Molality = number of gmoles of solute/kg of solvent Normality = number of gm. Equivalent /liter of solution Number of gm. Equivalent = weight of solute/equivalent weight of solute Equivalent weight of solute = molecular weight of solute/valence valence X weight of solute Therefore, Normality = molecular weight of solute X liter of solution Normality = Molarity x valence ppm = (weight of solute/weight of solution) x 106

VanderWaals Equation

(P + n

V2

)(V nb ) = nRT
RT m3 b= 1 C 8 PC , kmole
2 n a

Where VanderWaals constants 2 2 atm m 6 27 R TC a= 64 PC , kmole 2 Redlich Kwong Equation P = nRT

V nb

T 0.5V (V + nb )

Where Redlich Kwong constants R 2TC 2.5 atm m 6 K 0.5 RT m3 a = 0.42748 b = 0.086 C , 2 PC PC , kmole kmole T = absolute temperature of the gas; Pc = critical pressure; Tc = critical temperature.

PART A What are Dimensions and units? What is understood by a Dimensionally consistent equation? Illustrate by an equation. Explain the Basis of calculation used in chemical process calculations. How are solid, liquid and gas compositions expressed normally? 5. Name few methods of expressing quantity of a solute present in a solution (concentration). 6. Under what conditions a gas can be termed an Ideal gas? 7. Write Van der waals equation of state and write what each symbol represents. 8. Write Redlich-Kwong equation of state and write what each symbol represents. 9. Show that for ideal gases volume percentage, mole percentage and partial pressure percentage are all equal. 10. Define i) Normality ii) ppm 11. Define i) Molality ii) Molarity Units and Dimensions Fundamental quantities consists of four quantities, namely length, mass, time and temperature. These are called dimensions or basic units. Derived quantities consist of quantities derived from the fundamental quantities such as area, force, pressure, energy etc., Dimensions are our basic concepts of measurements such as length, time, mass, temperature and so on.Units are the means of expressing the dimensions such as feet or centimetres for length, or hours or seconds for time. Consistent units 1. 2. 3. 4.

A basic principle exits that equations must be dimensionally consistent. What the principle requires is that each term in an equation must have the same net dimensions and units as every other term to which it is added or subtracted or equated. The concept of dimensional consistency can be illustrated by an equation that represents gas behaviour and is known as van der Waals equation:

a P + 2 ( V b ) = nRT V

Inspection of the equation shows that the constant a must have the units of [(pressure) (volume) 2] in order for the expression in the first set of parentheses to be consistent throughout. If the units of pressure are atm and those of volume are m3, a will have the units specifically of [(atm) (m6)]. Similarly, b must have the same units as V or in this particular case the units of m3. If T is in K and n is in kg mol, the units of R are [(atm) (m3)/ (kg mol)(K)] . All equations must exhibit dimensional consistency.
Basis of calculation used in process calculations.

In any particular problem, the basis is the reference chosen for the calculations. A proper choice of basis frequently makes the problem much easier to solve. Sometimes when a number of bases seem appropriate, we may find it is best to use a unit basis or 1 or 100 of something, as for example, kilograms, hours, moles, cubic feet. For liquids and solids, in which a weight analysis is used, a convenient basis is often 1 or 100 kg; similarly, 1 or 100 moles is often a good choice for a gas. The reason for these choices is that the fraction or percent automatically equals the number of pounds, kilograms, or moles, respectively and one step in the calculations is saved.
Solid, liquid and gas compositions expressed normally

The composition of gases is always expressed in mole percent or mole fraction. Analysis of liquids and solids usually are given by mass (weight) percent or mass fraction, but occasionally by mole percent or mole fraction.
Air composition in mole % and weight %.

Composition of air: Component O2 N2 Total Mole % 21.0 79.0 100.0 Weight % 23 77 100.0

Numerical Value of R 0.082058

Units m 3 . atm L . atm or kmol . K mol . K J kPa . m 3 or g mol . K kmol . K kcal Btu or kmol . K lb mol . o R

R values:

8.31451

1.987216

Density: The density of a substance is defined as the mass per unit volume. Density for liquids and

solids do not change significantly at ordinary conditions with pressure, but they do change with temperature. In the case of gases, as the mass contained in a unit volume varies with the temperature and pressure, these two conditions must be specified. If not otherwise specified, the densities are presumed to be at standard conditions (S.C).

Specific gravity is the ratio of two densities - that of the substance of interest, to that of the

reference substance. The reference substance for liquids and solids normally water at 40C. The specific gravity of the gases frequently is referred to air at the same temperature and pressure of the gases, but may be referred to other gases also.

Ideal gas: Under the conditions such that the average distance between the molecules in a

substance is great enough to neglect the effect of the intermolecular forces and the volume of the molecules themselves, a gas can be termed an ideal gas. More properly an ideal gas is an imaginary gas that obeys exactly the following relationship. pV = RT Where p = absolute pressure; V = specific volume of the gas; R = ideal gas constant in appropriate units; T = absolute temperature of the gas.

Partial Pressure: In a gas mixture each component exerts a different pressure, depending on

the mole fraction of that component. This pressure exerted by each component is called partial pressure or pure component pressure. It is defines as, p i = p . yi

Where p i is the partial pressure of the i th component, p is the total pressure and xi is the mole fraction of i th component in the gas mixture.

Vapour pressure: The vapour pressure of a liquid is defined as the absolute pressure at

which the liquid and its vapour are in equilibrium at a given temperature.

Raoults law: Raoult proposed a law for an ideal solution. According to him, the vapour

pressure of the solvent in a solution is directly proportional to the mole fraction of the solvent. Vapour pressure of a solvent in the solution = (Vapour pressure of pure solvent) x (mole fraction of solvent). Only very ideal solutions obey Raoults law. An ideal solution may be defined as the one which obeys the Raoults law over the complete range of concentration and at all temperatures. Such solutions are formed by mixing the constituents in the liquid state without heat and volume changes. At low concentrations of gas in liquid, Raoults law does not hold good. For such non-ideal behaviour, Henrys law is found to be useful.

Henrys law : If p i is the partial pressure of the solute gas i,

p i = Hi . xi where xi is the mole fraction of i

th

component in the solution Hi is the Henrys law constant (note that

according to Raoults law, Hi should be equal to the vapour pressure for an ideal solution. Henrys law proposed for low concentration of gas in the liquid.

Pressure: The standard atmosphere is defined as the pressure equivalent to 1 atm. or 760mm Hg at O oC or other equivalent value. If a reading on column of a mercury as illustrated in

the figure, with the dish open to the atmosphere, the device is called a barometer and the reading of the atmospheric pressure is termed as barometric pressure. An open end manometer would measure a relative pressure (gauge pressure), since the reference for the open end is the pressure of the atmosphere at the open end of the manometer. On the other hand, closing off the end of the manometer and creating a vacuum in the end results in a measurement against a complete vacuum, or against no pressure.barometer A This measurement is called absolute pressure. The relation between the relative and absolute pressure is given by the following expression: gauge pressure + barometric pressure = absolute pressure. Vacuum refers to sub-atmospheric pressure. barometric pressure vacuum pressure = absolute pressure.