chemical Engineering Important laws in

subject wise
Presented by
Abdul Jabbar G
Chemical Engineer
Process Calculation
 Dalton’s Law
 Dalton's law, the statement that the total pressure of a mixture of gases is equal to the
sum of the partial pressures of the individual component gases.

Pt = P 1 + P2

 Pt = Total pressure, P1 & P2 = Partial pressures

 Dalton's law is empirical and only strictly true for ideal gases.
 Amagat's law
 The ideal gas at constant temperature and pressure the total volume of a gas mixture is
equal to the sum of the partial volumes
Vt = V1 + V2

 Vt = Total pressure, V1 & V2 = Partial Volumes

 Boyle's law
 The volume of a given mass of a gas is inversely proportional to its Pressure at constant Temperature
P ∝ 1/V
 Charles's law
 The volume occupied by a fixed amount of gas is directly proportional to its absolute temperature, if the
pressure remains constant.
V∝T
 Gay-Lussac’s law or Amonton’s law
 The absolute temperature and pressure of an ideal gas are directly proportional, under conditions of constant
mass and volume
P∝T
 Avogadro's law
 Equal volumes of all gases, at the same temperature and pressure, have the same number of
molecules.
V/n= constant
 IDEAL GAS LAW
 The product of the pressure and the volume of one gram molecule of an ideal gas is equal to
the product of the absolute temperature of the gas and the universal gas constant.

PV=nRT

 R is the ideal gas constant, which is also the universal gas constant or the product of the and
Boltzmann constant and Avogadro’s number.
 Assumptions
 The gas particles have negligible volume.
 The gas particles are equally sized and do not have intermolecular forces (attraction or
repulsion) with other gas particles.
 The gas particles move randomly in agreement with Newton's Laws of Motion.
Thermodynamics

 Zeroth law of Thermodynamics

 When a body, ‘A’, is in thermal equilibrium with another body, ‘b’, and also separately in thermal
equilibrium with a body ‘, C’, then body, ‘B’ and ‘C’, will also be in thermal equilibrium with each
other.
 First law of thermodynamics
 Heat is a form of energy, and thermodynamic processes are, therefore, subject to the principle of
conservation of energy. This means that heat energy cannot be created or destroyed. It can, however,
be transferred from one location to another and converted to and from other forms of energy.
ΔU = q + W
 ΔU = Change in internal energy of the system
 q = Algebraic sum of heat transfer between system and surroundings
 W = Work interaction of the system with its surroundings
 Limitations of 1st law of Thermodynamics
 It does not tell us about the direction of the flow of heat.
 It fails to explain why heat cannot be spontaneously converted into work.
 Applications of the first law of thermodynamics
 Isobaric process
 Adiabatic process
 Isochoric process
 Second law of thermodynamics
 Any spontaneously occurring process will always lead to an escalation in
the entropy (S) of the universe. In simple words, the law explains that an isolated
system’s entropy will never decrease over time.
 The second law is also known as the Law of Increased Entropy.

ΔSuniv > 0

 Where ΔSuniv is the change in the entropy of the universe.

Two statements on the second law of thermodynamics
1. Kelvin-plank Statement
2. Clausius Statement
 Kelvin- plank Statement
 It is impossible for a heat engine to produce a network in a complete cycle, if it exchanges heat
only with bodies at a single fixed temperature.
 Exceptions:
 If Q2 =0 (i.e., Wnet = Q1, or efficiency=1.00), the heat engine produces work in a complete cycle
by exchanging heat with only one reservoir, thus violating the Kelvin-Planck statement.
 Clausius’s Statement
 It is impossible to construct a device operating in a cycle that can transfer heat from a colder
body to a warmer one without consuming any work.
 Application of the second law of thermodynamics
 The second law of thermodynamics is applied in refrigerators
 The limitations of the Second Law of Thermodynamics are:
 The second law of thermodynamics only deals with the irreversibility of heat conversion to another
form.
 The second law of thermodynamics only deals with closed systems.

 The third law of thermodynamics

 Entropy of a perfect crystal at a temperature of zero Kelvin (absolute zero) is equal to zero or the
entropy of a system at absolute zero is constant or it is impossible for a process to bring the entropy
of a given system The to zero in a finite number of operations.
 Phase Rule
 Gibbs phase rule gives the degree of freedom (or the number of independent thermodynamic
properties ) of a system. These properties are Intensive properties only. They cannot be extensive
properties
F= C-P+2-r-s

 F=degree of freedom, C= number of compound, P=number of phases, r=number of independent

chemical reaction s= special constraint ( for immiscible solution & Azeotropes )
Fluid mechanics
 Newton's law of viscosity
 The shear stress is directly proportional to the velocity gradient.
 The equation of newton's law of viscosity is
τ = μ du/dy

 Where τ= shear stress, μ= viscosity, and du/dy= velocity gradient

 Pascal’s Law
 Intensity of pressure at a point in a fluid at rest is same in all direction
F = PA

 Applications of Pascal’s Law

 Hydraulic lift work on the principle of Pascal’s Law.
 It works based on the principle of equal pressure transmission throughout a fluid
(Pascal’s Law).
 Hydrostatic law
 Rate of increase of pressure of fluid at rest in vertical direction is equal to the specific weight of the fluid
 p = ρgh

 p is the pressure exerted by the liquid in N.m-2 or Pa

 ρ is the density of the liquid in kg.m-3,
 g is the acceleration due to gravity taken as 9.81m.s-2
 h is the height of the fluid column in m
 Archimedes’ Principle
 The upward buoyant force that is exerted on a body immersed in a fluid, whether partially or fully
submerged, is equal to the weight of the fluid that the body displaces and acts in the upward direction at
the center of mass of the displaced fluid.
Fb = ρ x g x V

 Fb is the buoyant force, ρ is the density of the fluid, V is the submerged volume, and g is the acceleration
due to gravity.
 Continuity equation/ Law of conservation of mass
 Law of conservation of mass is called continuity equation. It means quantity of fluid entering the
stream tube per unit time should be Equal to quantity of fluid leaving the stream

ρ1A1v1 = ρ2A2v2

Min=Mout

 M= mass, A= Area, v= velocity

 Use of Equation of Continuity
 The continuity equation provides very useful information about the flow of fluids and their
behaviour during their flow in a pipe or hose. Continuity Equation is applied on tubes, pipes,
rivers, ducts with flowing fluids or gases and many more.
 The continuity equation applies to all fluids, compressible and incompressible flow, Newtonian
and non-Newtonian fluids.
 Bernoulli’s Principle
 The total mechanical energy of the moving fluid comprising the gravitational potential energy
of elevation, the energy associated with the fluid pressure and the kinetic energy of the fluid
motion, remains constant or Bernoulli’s equation formula is a relation between
pressure, kinetic energy, and gravitational potential energy of a fluid in a container.
 Bernoulli’s principle can be derived from the principle of conservation of energy.

p1+ 1/2ρv21+ρgh1=p2+ 1/2ρv22+ρgh2.

 It is for ideal case. When you consider frictional losses then that is for real case
 Application of Bernoulli’s equation
 The Bernoulli equation can be applied to devices such as the orifice meter, Venturi meter, and
Pitot tube and its applications for measuring flow in open channels and inside tubes
 Bernoulli’s effects find many real-life applications, such as aero plane wings are used for
providing a lift to the plane..
MASS TRANSFER
 Fick’s Law of Diffusion
 Molar flux of a species relative to an observer moving with the average molecular velocity is
proportional to the concentration gradient of the species

J=−D dϕ/dx

 J= diffusion flux, D= diffusivity , ϕ =concentration & x= position

 Raoult’s Law
 The partial pressure of a component at a fixed temperature equals the product of its vapour pressure of
pure component and its mole fraction in the liquid phase

PA =P°A xA , PB =P°B xB

 PA = partial pressure of A.
 P°A =vapour pressure of pure A at that temperature
 xA =mole fraction of A in the liquid phase, Similarly, P B, P°B, xB
 Limitations of Raoult’s law
 Raoult’s law is valid only in the case of ideal solutions. However, ideal solutions are hard to find, and they
are rare. Different chemical components have to be chemically identical equally.
 Since many of the liquids that are in the mixture do not have the same uniformity in terms of attractive
forces, these types of solutions tend to deviate away from the law. There is either a negative or a positive
deviation. The negative deviation occurs when the vapour pressure is lower than expected from Raoult’s law
 Henry’s Law
 The amount of gas that is dissolved in a liquid is directly proportional to the partial pressure of that gas
above the liquid when the temperature is kept constant. The constant of proportionality for this relationship
is called Henry’s law constant (usually denoted by ‘kH‘).
P = kH.C
 P = partial pressure of the gas in the atmosphere above the liquid. C = concentration of the dissolved gas.
‘kH’ =Henry’s law constant of the gas.
 Limitations of Henry’s Law
 This law is only applicable when the molecules of the system are in a state of equilibrium.
 Henry’s law does not hold true when gases are placed under extremely high pressure.
 The law is not applicable when the gas and the solution participate in chemical reactions with each other.
Heat Transfer
 Fourier’s law ( The law of heat conduction)

 The negative gradient of temperature and the time rate of heat transfer is proportional to the area at
right angles of that gradient through which the heat flows.
 Three-dimensional form 𝑞=−𝑘▽𝑇
 q = local heat flux density ,k = conductivity of the material , .K-1 ▽T =Temperature gradient
 One- dimensional form 𝑞 𝑥 = − 𝑘 d 𝑇/ dx
 Newton's Law of cooling
 The rate of heat loss from a body is directly proportional to the difference in body temperature, and
its surroundings.
Q = h. A. (Tt – Tenv)

 Q = rate of heat transfer out of the body, H = heat transfer coefficient, A = heat transfer surface area,
T = temperature of the object's surface, Tenv = temperature of the environment, Tt = time-dependent
temperature
 Stefan Boltzmann law(Law of Radiation
 The amount of radiation emitted per unit area per unit time (total emissive power) of a black body at
absolute temperature T is directly proportional to the fourth power of the temperature.
Eb = σT4
 σ is Stefan’s constant = 5.67 × 10-8 W/m2 k4
 Planck's law
 The monochromatic emissive power of a black body dependent on both absolute temperature of a black
body and wavelength of emission
 Kirchhoff’s Law of Radiation
 Whenever a body in thermal equilibrium with its surrounding its emissivity is equal to its absorptivity
 Wien’s displacement law
 black body radiation has different peaks of temperature at wavelengths that are inversely proportional to
temperatures.
λmax T= constant=2898 μmk
Chemical Reaction Engineering
 Rate law
 The Rate law (also known as the rate equation) for a chemical reaction is an expression that provides a
relationship between the rate of the reaction and the concentrations of the reactants participating in it
Rate = k[A]x[B]y
 [A] & [B] =concentrations of the reactants A and B , x & y denote the partial reaction orders for reactants ,
A & B (which may or may not be equal to their stoichiometric coefficients a & b), The proportionality
constant ‘k’ is the rate constant of the reaction.
 Hess’s Law
 The enthalpy change in a chemical or physical process is the same whether the process is carried out in one
step or in several steps or Hess’s law states that the increase in enthalpy in a chemical reaction i.e., reaction
heat at constant pressure is independent of the process between the initial and final states. Hess’s law is one
of the important outcomes of the first law of thermodynamics.
ΔHR= ΔH1+ ΔH2….
 Le Chatelier's principle
 A change in one of the variables that describe a system at equilibrium produces a shift in the position of the
equilibrium that counteracts the effect of this change.
 changing the concentration of one of the components of the reaction
 changing the pressure on the system
 changing the temperature at which the reaction is run.
 Mechanical operation
 Rittinger’s Law
 It states that the energy required for size reduction is directly proportional to
the change in surface area.
 Kicks Law
 It states that the energy required to reduce an amount of material is directly
proportional to its the size reduction ratio, the energy required for grinding
will be the same regardless of the original size of its particles.
 Bond’s Law
 It states that energy used for size reduction of the particle is proportional to
the square root of the diameter of the particle produced.