Scribd Logo
Upload

Welcome to Scribd!

  • 88 views

    Thermochemistry: Chemical Thermodaynamics

    Uploaded by

    Norhaszan

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd

    Thermochemistry: Chemical Thermodaynamics

    Uploaded by

    Norhaszan
    88 views36 pages

    Original Title

    Chemical Thermodynamics 2

    Copyright

    © © All Rights Reserved

    Available Formats

    PPT, PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    88 views36 pages

    Thermochemistry: Chemical Thermodaynamics

    Uploaded by

    Norhaszan

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 36

    Thermochemistry

    CHEMICAL
    THERMODAYNAMICS

    Copyright © The McGraw-Hill Companies, Inc.  Permission required for reproduction or display.
    The following items will be discussed :

    6-1- The nature of energy and types of energy

    6-2- Energy changes in chemical reactions

    6-3- Introduction to thermodynamics

    6-4- Enthalpy of chemical reactions

    6-5-Calorimetry; the measurement of heat change.


    6-6- Standard enthalpy of formation and reaction

    6-7- Heat of solution and dilution


    A LOOK AHEAD

    1-The study of the nature and the different types of energy.


    2- The study of heat change in chemical reactions, which is thermo
    chemistry . The vast majority of reactions are either endothermic
    (absorbing heat) or exothermic (releasing heat).
    3-The thermo chemistry is a part of a broad subject called the first
    law of thermodynamics, which is based on the law of conservation
    of energy. The change in internal energy can be expressed in terms
    of the changes in heat and work done of a system.
    4- The measure of the heat of reaction or calorimetry under
    constant-volume and constant-pressure, and the meaning of
    specific heat and heat capacity, quantities used in experimental
    work.

    Tro, Chemistry: A Molecular Approach 3


    A LOOK AHEAD

    5- Knowing the standard enthalpies of formation of reactants and


    products enables us to calculate the enthalpy of a reaction. Discuss
    ways to determine these quantities either by the direct method from
    the elements or by the indirect method, which is based on Hess’s
    law of heat summation.
    6- Finally, the study the heat changes when a solute dissolves in a
    solvent (heat of solution) and when a solution is diluted (heat of
    dilution).
    Every chemical reaction obeys two fundamental laws;
    the law of conservation of mass and the law of
    conservation of energy. The mass relationships between
    reactants and products are discussed .
    Tro, Chemistry: A Molecular Approach 4
    6-4- Enthalpy of chemical reactions
    Enthalpy and the First Law of Thermodynamics
    E = q + w
    At constant volume
    At constant pressure:
    V = 0 W = - PV
    qp = H and w = -PV W = P X0 = 0
    E = qv – 0 = qv
    E = H - PV qv = 
    H = E + PV E = 

    6.4
    * The two factors that determine the thermodynamic
    favorability are the enthalpy and the entropy.
    * The enthalpy is a comparison of the bond energy of the
    reactants to the products.
    * bond energy = amount needed to break a bond.
    H
    * The entropy factors relates to the
    randomness/orderliness of a system
    S
    * The enthalpy factor is generally more important than
    the entropy factor

    Tro, Chemistry: A Molecular Approach 6


    Enthalpy of Reactions

    Because most of reactions are constant pressure


    processes, we can equate the heat change to the change in
    enthalpy.
    For any reaction such as: A (reactant) B (product)
    the change in enthalpy, called the enthalpy of reaction,
    ΔH = H (products) – H (reactants)

    Tro, Chemistry: A Molecular Approach 7


    Entropy
    entropy is a thermodynamic function that increases as
    the number of energetically equivalent ways of
    arranging the components increases, S
    S generally J/mol
    S = k ln W
    k = Boltzmann Constant = 1.38 x 10-23 J/K
    W is the number of energetically equivalent ways,
    unitless

    Tro, Chemistry: A Molecular Approach 8


    Enthalpy (H) is used to quantify the heat flow into or out of a
    system in a process that occurs at constant pressure.
    H = H (products) – H (reactants)
    H = heat given off or absorbed during a reaction at constant pressure

    Hproducts < Hreactants Hproducts > Hreactants


    H < 0 H > 0 6.4
    Thermochemical Equations

    Is H negative or positive?

    System absorbs heat

    Endothermic

    H > 0

    6.01 kJ are absorbed for every 1 mole of ice that


    melts at 00C and 1 atm.

    H2O (s) H2O (l) H = 6.01 kJ


    6.4
    Thermochemical Equations

    Is H negative or positive?

    System gives off heat

    Exothermic

    H < 0

    890.4 kJ are released for every 1 mole of methane


    that is combusted at 250C and 1 atm.

    CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H = -890.4 kJ


    6.4
    Thermochemical Equations

    • The stoichiometric coefficients always refer to the number


    of moles of a substance
    H2O (s) H2O (l) H = 6.01 kJ

    • If you reverse a reaction, the sign of H changes


    H2O (l) H2O (s) H = -6.01 kJ

    • If you multiply both sides of the equation by a factor n,


    then H must change by the same factor n.

    2H2O (s) 2H2O (l) H = 2 x 6.01 = 12.0 kJ

    6.4
    Thermochemical Equations

    • The physical states of all reactants and products must be


    specified in thermochemical equations.
    H2O (s) H2O (l) H = 6.01 kJ
    H2O (l) H2O (g) H = 44.0 kJ

    How much heat is evolved when 266 g of white


    phosphorus (P4) burn in air?
    P4 (s) + 5O2 (g) P4O10 (s) H = -3013 kJ

    1 mol P4 3013 kJ
    266 g P4 x x = 6470 kJ
    123.9 g P4 1 mol P4

    6.4
    Worked Example 6.3
    A Comparison of H and E

    2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) H = -367.5 kJ/mol


    E = H - PV At 25 0C, 1 mole H2 = 24.5 L at 1 atm
    PV = 1 atm x 24.5 L = 24.5 L.atm = 2.5 kJ

    E = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol

    In case of ideal gases and at constant temperature


    E = H – RT n

    6.4
    Worked Example 6.4
    6-5- Calorimetry

    The specific heat (s)


    Heat capacity (C)

    Heat (q) absorbed or released


    q = m x s x t
    q = C x t
    6-5- Calorimetry : the measurement of heat change .
    The specific heat (s) of a substance is the amount of heat (q) required to
    raise the temperature of one gram of the substance by one degree
    Celsius.

    The heat capacity (C) of a substance is the amount of heat (q) required
    to raise the temperature of a given quantity (m) of the substance by one
    degree Celsius.

    C=mxs
    Heat (q) absorbed or released:
    q = m x s x t
    q = C x t
    t = tfinal - tinitial
    6.5
    How much heat is given off when an 869 g iron bar cools
    from 940C to 50C?

    s of Fe = 0.444 J/g • 0C

    t = tfinal – tinitial = 50C – 940C = -890C

    q = mst = 869 g x 0.444 J/g • 0C x –890C = -34,000 J

    6.5
    Worked Example 6.5
    Worked Example 6.6
    6.5
    Chemistry in Action:
    Fuel Values of Foods and Other Substances
    C6H12O6 (s) + 6O2 (g) 6CO2 (g) + 6H2O (l) H = -2801 kJ/mol

    1 cal = 4.184 J
    1 Cal = 1000 cal = 4184 J

    Substance Hcombustion (kJ/g)

    Apple -2

    Beef -8

    Beer -1.5

    Gasoline -34
    6-6- Standard enthalpy of formation and reaction

    Because there is no way to measure the absolute value of the


    enthalpy of a substance, must I measure the enthalpy change for
    every reaction of interest?

    Establish an arbitrary scale with the standard enthalpy of formation


    (H0) as a reference point for all enthalpy expressions.

    Standard enthalpy of formation (Hf0) is the heat change that results


    when one mole of a compound is formed from its elements at a
    pressure of 1 atm.

    The standard enthalpy of formation of any element in its most stable


    form is zero.

    H0f (O2) = 0 H0f (C, graphite) = 0


    H0f (O3) = 142 kJ/mol H0f (C, diamond) = 1.90 kJ/mol
    6.6
    6.6
    The standard enthalpy of reaction (Hrxn 0
    ) is the enthalpy of
    a reaction carried out at 1 atm which can be determined by:
    The direct method
    aA + bB cC + dD
    Hrxn
    0
    = [ cH0f (C) + dH0f (D) ] - [ aH0f (A) + bH0f (B) ]

    Hrxn
    0
    =  nH0f (products) -  mHf0 (reactants)

    The indirect method


    Hess’s Law: When reactants are converted to products,
    the change in enthalpy is the same whether the reaction
    takes place in one step or in a series of steps.

    (Enthalpy is a state function. It doesn’t matter how you get


    there, only where you start and end.)
    6.6
    C (graphite) + 1/2O2 (g) CO (g)
    CO (g) + 1/2O2 (g) CO2 (g)
    C (graphite) + O2 (g) CO2 (g)

    6.6
    Calculate the standard enthalpy of formation of CS2 (l)
    given that:
    C(graphite) + O2 (g) CO2 (g) Hrxn 0
    = -393.5 kJ
    S(rhombic) + O2 (g) SO2 (g) Hrxn
    0
    = -296.1 kJ
    CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) H0rxn = -1072 kJ
    1. Write the enthalpy of formation reaction for CS2

    C(graphite) + 2S(rhombic) CS2 (l)


    2. Add the given rxns so that the result is the desired rxn.
    C(graphite) + O2 (g) CO2 (g) Hrxn
    0
    = -393.5 kJ
    2S(rhombic) + 2O2 (g) 2SO2 (g) Hrxn0
    = -296.1x2 kJ
    + CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) H0rxn = +1072 kJ

    C(graphite) + 2S(rhombic) CS2 (l)


    6.6 H0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ
    Benzene (C6H6) burns in air to produce carbon dioxide and
    liquid water. How much heat is released per mole of
    benzene combusted? The standard enthalpy of formation
    of benzene is 49.04 kJ/mol.
    2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

    Hrxn
    0
    =  nH0f (products) -  mHf0 (reactants)

    Hrxn
    0
    = [ 12H0f (CO2) + 6H0f (H2O)] - [ 2Hf0 (C6H6) ]

    Hrxn
    0
    = [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ

    -5946 kJ
    = - 2973 kJ/mol C6H6
    2 mol

    6.6
    Worked Example 6.9
    Worked Example 6.10
    6-7- Heat of solution and dilution
    The enthalpy of solution (Hsoln) is the heat generated or
    absorbed when a certain amount of solute dissolves in a
    certain amount of solvent.
    Hsoln = Hsoln – Hcomponents

    Which substance (s) could


    be used for melting ice?

    Which substance (s) could


    be used for a cold pack?

    6.7
    The Solution Process for NaCl

    Hsoln = Step 1 + Step 2 = 788 – 784 = 4 kJ/mol


    6.7
    Hsoln = U – Hhydration
    NaCl (s) Na+ (g) + Cl- (g) U = 788 kJ / mol

    Na+ (g) + Cl- (g) Na+ (aq) + Cl- (aq) H = - 784


    kJ/mol
    ______________________________________________________
    NaCl (s) Na+ (aq) + Cl- (aq) H = 4 kJ/mol
    The heat of dilution is the heat change associated
    with the dilution process , if a certain solution
    process is endothermic and the solution is diluted,
    more heat will be absorbed by the same solution
    from the surrounding.
    In case of dilution H2SO4 this process is so
    exothermic that you must never attempt to dilute
    the concentrated acid by adding water to it. The
    recommended procedure is to add the concentrated
    acid slowly to the water while constantly stirring.
    Chemistry in Action: Bombardier Beetle Defense

    C6H4(OH)2 (aq) + H2O2 (aq) C6H4O2 (aq) + 2H2O (l) H0 = ?

    C6H4(OH)2 (aq) C6H4O2 (aq) + H2 (g) H0 = 177 kJ/mol

    H2O2 (aq) H2O (l) + ½O2 (g) H0 = -94.6 kJ/mol

    H2 (g) + ½ O2 (g) H2O (l) H0 = -286 kJ/mol

    H0 = 177 - 94.6 – 286 = -204 kJ/mol


    Exothermic!

    You might also like