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Thermodynamics

Thermodynamics

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Published by ajayyashpal
THERMODYNAMICS
THERMODYNAMICS

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Published by: ajayyashpal on Mar 17, 2013
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 Sir. AJAY YASHPAL(98187 02707) Education Point Sir. Anoop Behl
Chemical Energetics:
The branch of science which deal with energy change in physical and chemicalreactions.
System:
A specified portion of universe which is under observation is called system. It is of two types:(i)
 
Heterogeneous system: If all the parts of the system have different physical and chemical properties.(ii)
 
Homogenous system: If all the parts of the system have same physical and chemical properties.
Surrounding:
The rest part of the universe which is not under investigation.Type of system:
1.Isolated:
A system that can not exchange energy or matter from surrounding.
2. Close system:
It can exchange energy only with surroundings.
3. Open system:
It can exchange both energy as well as matter with surroundings.
State variables:
The measurable properties required to describe the state of the system example; temperature, pressure, volume.
State function:
A state function is a property of the system whose value depends only upon the state of thesystem and is independent of the path by which the path is reached.
Mode of transference of energy:
In energetic two main mode of transference of energy are:
(i)
 
Heat change:
Energy is always exchanged with surrounding except in case of isolated system whenthere is change in temperature between system and surroundings.
(ii)
 
Work done:
It is exchange of energy of system with surrounding when there is change in pressure.Internal energy of system; it is the sum of all different kind of energy associated with molecule such as energyof translation ,rotation ,and vibration, electric energy ,energy due to molecular interaction.
Internal energy change:
it is difference between energy of reactant and product.It may also be defined as amount of heat evolved or absorbed in chemical reaction at constant temperature andat constant volume. It is denoted by
E.
E=E
 product
-E
reactants
 
Enthalpy (H):
it may be defined as amount of heat evolved or absorbed in chemical reaction at constanttemperature and pressure. Or, the sum of the internal energy and the product of its pressure and volume.
Enthalpy change:
It is measure of heat change taking place during a process at constant pressure.H=E+PV and
∆ H=∆ E+P∆ V
 Enthalpy of reaction:
The change during a chemical reaction when number of moles of reactants and product being same as indicated by the balanced chemical equation.
Enthalpy of formation:
Enthalpy change when one mole of a compound is formed from its elements.
Standard Enthalpy of formation:
Enthalpy change when one mole of a compound is formed from itselements, all the substance being in their standard state (1 atm. and 298K) Note: By convention the heat of formation of every element in its standard state is arbitrary assumed to be zero.
H
0(for the reaction)
= H
0(products)
-H
0(reactants)
Enthalpy of combustion:
The amount of heat change when one mole of a substance is completely burnt onexcess of oxygen or air is called heat of combustion.
Calorific value:
The amount of heat produced when one gram of a substance is completely burnt. The amountof heat is taken in calories or joules.
Enthalpy of solution:
The heat change when one mole of substance is dissolved in a specified quality of solvent at a given temperature is called heat of solution.
Enthalpy of neutralization:
The heat change when one gram equivalent of acid is completely neutralized by a base or vice-versa in dilute is called heat of neutralization. Note: Heat of neutralization of all strong acids by strong bases is always -57.1KJ irrespective of the nature of acids or the base.
Enthalpy of fusion:
The amount of heat change when one mole of a solid substance is converted into its liquidstate at its melting point.
Enthalpy of vapourisation:
The amount of heat change when one mole of a liquid substance is converted intoits gaseous state at its boiling point.
 
 Sir. AJAY YASHPAL(98187 02707) Education Point Sir. Anoop Behl
Enthalpy of sublimation:
The amount of heat change when one mole of a solid substance is directly convertedinto its gaseous.
First law of Thermodynamics:
It states that energy can neither be created nor destroyed, although, it can beexchanged from one state to another or total energy
 
of universe is constant.
Hess’s law:
It states that the enthalpy change in a particular reaction is always constant and is independent of the path in which the reaction takes place.This Law means that amount of heat evolved or absorbed in a chemical reaction is always constantwhether the reaction is taking place in one step or in number of steps. This also means that a chemical reactioncan be summed, subtracted, multiplied or divided by any constant like algebraic equations.
 
One more conclusion can be drawn from the Hess’s law that the same amount of energy is required to build
a molecule from its constituents that was released or absorbed during breaking of molecules into its constituentsor vice versa.
Some main uses of Hess’s law:
 1.
 
Determination of enthalpy of formation
: It is a very useful property or use of Hess’s law
 because there are so many compounds which can not be made from their constituent elements. For example; Benzene, polyethylene, sugar, etc.2.
 
Determination of enthalpy of transition: It means energy evolved or absorbed duringchange in physical state of any substance. For example: conversion of liquid togas or vapours, changing crystal structure.3.
 
Predicting enthalpies of various reactions: As stated earlier, chemical equations can besummed, subtracted, multiplied or divided by any numerical factor.4.
 
Determination of Bond energy: Bond energy is the energy required to break the bonds below the atoms in a molecule in gaseous state. It is also called bonddissociation energy. Or the average energy required breaking the bonds of a giventype in one mole of the gaseous molecule.
Spontaneous process:
The process which can take place by it self under the given set of conditions once it has been initiated if necessary for example, fall of water from higher to lower level, whena candle is lighted it remains on burning till the whole wax is not burnt, a hot bodycools up to its surroundings automatically, when exposed to surroundings, etc.
Note: -
Spontaneous processes do not mean that the process is instantaneous or very fast, it may take a verylong time for example, conversion of a dead body to fossil fuel.
Non-Spontaneous process:
The process, which is not spontaneous, that is which require initiation in each andafter every step. For example, water gong up from lower to higher level withcontinuous helps of a motor, a car runs on roads if fuel is burning in its enginecontinuously.
Driving force:
The force or energy required initiating the process.
Why some processes are Spontaneous and some Non-Spontaneous:
 Every thing in this universe tries to gain minimum energy and maximum stability are spontaneous whilethose going towards higher energy content or towards lesser stability are Non-Spontaneous.
Why some chemical reactions are reversible in nature:
 There are so many reactions in nature which are reversible in nature, the reason behind that manyspontaneous reactions are exothermic and if products formed are not in their maximum stable state than the heat produced will be enough for them to convert back to the reactants but all the heat can not be utilized because of heat lost so, some products always remain in the reaction mixture along with reactants this makes a reactionreversible.
Do all the Exothermic reactions are spontaneous:
 
 
 Sir. AJAY YASHPAL(98187 02707) Education Point Sir. Anoop BehlMaximum numbers of spontaneous processes are exothermic or vice-versa, because reaction movestoward lower energy content but
H is not only the criterion of spontaneity, reactions also move towardsmaximum randomness or disorder. So, reactions move towards:1). Minimum energy,2). Maximum Stability;3). Maximum randomness or disorder.
Entropy (s):
The property of a system used to measure the degree of disorder or randomness of system.
S = S (products) -
S (reactants). Reactions move towards +ve sign.Also,
S = Q / T or 
H / T. Q
heat supplied. Its unit is jK 
-1
.
Physical meaning of entropy
Entropy is a measure of randomness of system, i.e., where the randomness is higher reactions move there. Assolids have ordered arrangement of particles, liquid and gaseous particles are unordered but disorder in liquid islimited but in gases it has no limit. A particle of gas can have any velocity and may be any where in thecontainer. So, gases have maximum randomness than liquid and liquids have higher than solids. So, reactionstry to move towards where gaseous or liquid products are more.
Second law of Thermodynamics:
It states that entropy of universe increases after every spontaneous processor natural process.
Free energy:
It is defined as the maximum amount of energy available to a process during a process that can beconverted to useful work.OR The amount of energy that remained unused by the system after getting minimum energy, maximumstability, and maximum randomness.OR Simply, It is a measure of capacity of a system to do work. It is denoted by
G.Thus,
G =
H -T
S
H Enthalpy change.T Temperature in Kelvin
S Entropy change.
Effect of temperature and tendency of reaction to occur in forward direction
Type of reaction Sign of 
H Sign of T
S
G Behavior 
Exothermic- + - Spontaneous- - - (at low temp.) Spontaneous+ (at high temp.) Non- SpontaneousEndothermic+ - + Non- Spontaneous+ + + (at low temp.) Non- Spontaneous- (at high temp.) SpontaneousStandard free energy:
The free energy change when the reactants are in their Standard states (i.e., at 298K and1atm) and are converted to the products in their Std. States.
Standard free energy of formation:
Change in free energy when 1 mole of a substance is formed from itsconstituent elements in their Std. States.
otsreac  f  o products  f  o  f  
GGG
)tan()(
 
Actually, free energy or Gibb’s free energy is the amount of energy that can be used to do useful work 
 but work may be of two types: Expansion work (Pressure-Volume work) Non-Expansion work.So,
G =
H - T
S
G = - n f E
ocell
{Electric work}.

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