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What is thermochemistry?
It is a branch of thermodynamics that deals with the heat involved in chemical and physical change and specially with the concept of enthalpy H. H enthalpy means the heat involved at constant pressure
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Thermochemistry
Introduction
In order to observe and measure a change in energy, we must define the SYSTEM that
Every thing else relevant to the change is defined as the SURROUNDINGS. Each particle in the system has potential and kinetic energy, and the sum of these energies for all the particles in the system is the INTERNAL ENERGY. Usually designated by the letter E or U. we shall use E.
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Thermochemistry
Thermochemistry is the study of the energy changes taking place during chemical reactions. Every substance contains stored chemical energy, called enthalpy, mainly by virtue of chemical bonds. Absolute enthalpy is hard to measure, but enthalpy changes during reactions are easy to measure because there will be an observable energy exchange between the chemicals and the surroundings.
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Specific heat capacity The heat needed to the temperature of 1 g of a substance by 1 C. Symbol: c, units: J/(gC). Heat capacity The heat needed to the temperature of an object by 1 C. Symbol: C (=c x m), units: J/C Heat of reaction The heat released during a chemical reaction. Symbol: none, units: J.
Molar heat of reaction The heat released during a chemical reaction per mole of reactant. Symbol: H, units: J/mol.
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Heat Calculations
To determine the amount of heat a substance produces or absorbs we often use q = mcT q: heat in J, c: specific heat capacity in J/(gC), m: mass in g, T: temperature change in C, This equation makes sense if you consider units Sample problem: (must know water = 4.18 J/gC) When 12 g of a food was burned in a calorimeter, the 100 mL of water in the calorimeter changed from 20C to 33C. Calculate the heat released.
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Thermochemistry
More Questions
5 g of copper was heated from 20C to 80C. How much energy was used to heat the Cu? If a 3.1 g ring is heated using 10.0 J, its temp. rises by 17.9C. Calculate the specific heat capacity of the ring. Is the ring pure gold?
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Thermochemistry
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Thermochemistry
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Thermochemistry
The energy associated with a change such as: reactants products ( must return to starting T i.e as started with reactants) The internal energy E of this system has changed . To determine this change E we measure the difference between the systems internal energy after the change (E final) and before the change (E initial) : E = E final - E initial = E products E reactants Note that refer to the final state of the system MINUS the initial state. ALWAYS ONE FACT: The total energy of the system and surrounding is constant (conserved). This means that a change in the energy of the system is always accompanied by an opposite change in the energy of the surroundings.
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The energy of the system decreases E is negative in other words E final < E initial E < 0
The energy of the system increases E is positive which means: E final > E initial E > 0
Note that the change in energy is always a transfer of energy from system to surroundings, or vice versa
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energy transfer (mechanical, electrical, etc) involve some type of WORK (w). The total change in a systems internal energy is the sum of the energy transferred as heat and / or work. E = q + w ( value of q and w can be either negative
transferred between a system and its surroundings as a result of a difference in their temperatures only. All other forms of
or positive) We define the sign of the energy transfer from the systems perspective only. Energy coming into the system is positive Energy going out from the system is negative
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There are four simple cases: a-Two that involve only heat transfer b-Two that involve only work
1. Heat transfer as Heat only. For a system that does no work but transfers energy only as heat (q). i.e w = 0 therefore : E = q + w = q + 0 = q Case 1: Heat flowing out from a system. e.g. glass of hot water on the table. The water transfers energy as heat to the surroundings until the T of water equals that of surroundings. The systems energy decreases as heat flows out from the system, so the final energy of the system is less than its initial energy. Heat was lost by the system , therefore, q is negative
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Thermochemistry
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E < 0
E =w
Zn( s ) 2H
aq
We define the system as the atoms that make up substances. In the initial state, the systems internal energy is that of the atoms in the form of the reactants; metallic Zn and aqueous H+ and Cl- ions. In the final state, the systems internal energy is that of the same atoms in the form of the products, H2 gas and aqueosZn2+ and Cl- ions. As H2 is formed, some of the internal energy is used by the system to do work on the surroundings and push the piston outward.
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Thermochemistry
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The system is loosing energy as work is done. The internal energy of the system decreases as the reactants form products because the H2 gas does work (w) on the surroundings
by pushing back the piston. The reaction vessel is insulated, so q = 0 since Einitial > E final then E < 0 , and the sign of w is negative The H2 gas is doing pressure-volume work (PV work). This is a type of work in which a volume changes against an external pressure.
Thermochemistry 17
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+ + 26-Nov-13
+ + -
+
Depend on sizes of q and w
Depend on sizes of q and w
Thermochemistry 18
Sign
Units of energy
SI unit of energy is the joule (J). This is a derived unit composed of three basic units: 1 J = 1 kg.m2/s2 Both heat and work are expressed in joules. See how it applies to work. [ F=force , d = distance] Work = F x d . A force changes the velocity of (accelerates) a mass. Velocity has units of meters per second (m/s) so acceleration (a) has units of m/s2. Force therefore has of mass (m in kg) x acceleration F= m x a in units of kg.m/s2 Therefore w = F x d has units of (kg.m/s2) x m = kg.m2/s2 =J 1 cal = 4.184 J i.e 1J=1/4.184 = 0.2390 cal 1 kJ =1000J = 0.239 kcal = 239 cal
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w+q
We have q= -324 J & w=-451 J E=-325J + (-451 J)=-776.1 J = -0.771 kJ To convert to calories we divide by 4.182 Therefore E=-0.776 kJ x (1 kcal/4.182 kJ) =
= -0.185 kcal
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Remember
Thermodynamics is the science of the relationship between heat and other forms of energy Thermochemistry is the science of the quantity of heat absorbed or evolved by chemical reactions. Types of energy: Kinetic energy Potential energy Chemical energy Heat energy Electric energy Radiant energy
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Energy
There are three broad concepts of energy: Kinetic energy is the energy associated with an object by virtue of its motion. Potential energy is the energy an object has by virtue of its position in a field of force. Internal energy is the sum of the kinetic and potential energies of the particles making up a substance.
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Thermochemistry
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Heat of reaction
In chemical reactions, heat is often transferred from the system to its surroundings or vice versa. Heat flows from a region of higher temperature to one lower temperature . Once the temperature becomes equal, heat flow stops. Heat of reaction is the value of q required to return a system to the given temperature at the completion of reaction. Exothermic process Endothermic process
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Thermochemistry
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and heat (q). The work done by an expanding gas is equal to P (external pressure - atmospheric) x V or (Vfinal - Vinitial)
P P W = -PV
Note that ( w) is negative because the work was done on the surroundings and the system loses energy
V
final state
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Thermochemistry
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But to determine W = -PV is not always possible, a thermodynamic variable called enthalpy eliminates the need to consider PV work separately. The enthalpy of a system is defined as the internal energy plus the product of the pressure and volume. H= E + PV the change in enthalpy H is then equal to the change in internal energy plus the product of the constant P and the change in the volume i.e H= E + PV
(w)=
- PV we get:
Thus the change in enthalpy equals the heat gained or lost at a constant pressure. With most changes occurring at constant P , H is more relevant than E , and easier to find; to find H measure qp.
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between enthalpies of products and reactants. Because the Hproducts can be either more or less than Hreactants , the sign of H reaction indicates whether heat
is absorbed or released in the change. We determine the sign of H by imagining the heat as a reactant or product.
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Because heat is released to the surroundings, the products (1 mol of CO2 and 2 mol of H2O ) must have less enthalpy than the reactants (1 mol CH4 and two mol of O2). Therefore, H = (Hproducts- Hreactants) is negative
CO2+2H2O
Enthalpy H
CH4+2O2
Enthalpy H
H final
H initial
H < 0
Heat out
H > 0
Heat in
H initial
An exothermic (heat out) process releases heat to the surrounding and always is associated with a decrease in enthalpy of the system
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An endothermic (heat in) process absorbs heat and results in an increase in the enthalpy of the system. e.g. Heat + H2O(solid H2O(l) heat flows into the system from the surroundings. Notice heat appears as a reactant. Because heat is absorbed , the enthalpy of the liquid water is higher than that of solid water, therefore:
For endothermic processes :Hfinal > Hinitial and H > 0
Please note that the value of an enthalpy change refer to the reactants and products at the same
temperature.
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Thermochemistry
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Remember
Sign conventions for Work and Heat Process Work done by the system on the surroundings Work done by the system by the surroundings Heat absorbed by the system from the surroundings (endothermic process) Heat absorbed by the surroundings from the system (exothermic process)
Sign
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Thermochemistry
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melts
Heat of vaporization Hvap: Heat associated with vaporization of one mole of a substance.
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forward reaction has the opposite sign of the reverse reaction. 2H O2( g ) 2H 2O( g ) H 572 kJ 2( g ) 2H 2O( g ) 2H O2( g ) H 572 kJ 2( g )
Thermochemistry 34
2- Magnitude: the magnitude of H is proportional to the amount of substances reacting. Formation of 1 mole of water from its elements
Problem: The major source of Al in the world is bauxite ( mostly aluminium oxide). Its thermal decomposition can be represented by: Al2O3 (s) 2Al + O2 H =1676 kJ How many grams of Al can be produced from 1.000 x 103kJ. Solution: If 1676 kJ produced 2 x 26.98, then 1000 kJ will produce =(1000 x 26.98 x 2)/1676 = 32.20 gm of Al
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Thermochemistry
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summation: the enthalpy change of an overall process is the sum of the enthalpy changes of its individual steps. Let us see how we apply this law e.g. in the case the oxidation of sulphur trioxide.
Thermochemistry 37
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Hesss Law
For any chemical change made in several steps, the net H is equal to the sum of the H values of the separate steps
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Thermochemistry
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H1 296 .8 kJ H 3 ?
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Thermochemistry
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H1 296.8 kJ
1 (equation 2 2SO2 ( g ) O2( g ) 2SO3( g ) H 2 198.4 kJ ) 2 1 1 SO2( g ) O2( g ) SO3( g ) H 2 99.2kJ 2 2 _______________________________________________ 1 equation 3 S ( s ) O2( g ) SO2( g ) O2( g ) SO2( g ) SO3 H 3 ? 2 adding the H we get : 1 H 3 H1 H 2 296.8 kJ (99.2 kJ ) 396.0 kJ 2
Once again the key point is that H
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is a state function
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Another example
e.g. find H for the reaction: 2 CH4(g) + 3 O2(g) 2 CO(g) + 4 H2O(l) using the following data:
CH4(g) + 2 O2(g) 2 CO(g) + O2(g) CO2(g) + 2 H2O(l) H = -890 kJ 2 CO2(g) H = -566 kJ
.(1)
(2)
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Thermochemistry
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Continue
Multiply equation (1) by 2 , and reaction (2) by -1 we get: 2 CH4(g) + 3 O2(g)
2 CH4(g) + 4 O2(g) 2 CO2(g) + 4 H2O(l) after multiplication H = -1780 kJ 2 CO2(g) 2 CO(g) + O2(g) H = +566 kJ after multiplication by -1 2 CH4(g) + 3 O2(g) 2 CO(g) + 4 H2O(l) H = -1214 kJ
2 CO(g) + 4 H2O(l)
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Thermochemistry
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Other examples:
H o f
0 -635.1 0 -92.3 0 0.3 143 ( note it is positive)
Thermochemistry 44
O3
Step 2 These atoms combine to form HCl molecules 2 H (g) + 2 Cl (g) 2 HCl (g) In the first step, the H-H and Cl-Cl bonds are broken. In both cases, one mole of bonds is broken. When we look up the single bond energies for the H-H and Cl-Cl bonds, we find them to be +436 kJ/mol and + 243 kJ/mol, therefore for the first step of the reaction: H1 = +(436 kJ + 243 kJ) = +679 kJ Bond breaking requires energy, so we expect the value for H to be positive for this step. In the second step of the reaction, two moles of H-Cl bonds are formed. Bond breaking liberates energy, so we expect the H for this portion of the reaction to have a negative value. Using the table, the single bond energy for one mole of H-Cl bonds is found to be 431 kJ: 46 26-Nov-13 H2 = -2(431 kJ) Thermochemistry = -862 kJ
By applying Hess's Law, H = H1 + H2 H = +679 kJ - 862 kJ H = -183 kJ Answer The enthalpy change for the reaction will be H = -183 kJ.
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Thermochemistry
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Assignments
1) Calculate H for the reaction: C2H4 (g) + H2 (g) C2H6 (g), from the following data. C2H4 (g) + 3 O2 (g) 2 CO2 (g) + 2 H2O (l) H = -1411. kJ C2H6 (g) + 3 O2 (g) 2 CO2 (g) + 3 H2O (l) H = -1560. kJ H2 (g) + O2 (g) H2O (l) H = -285.8 kJ 2) Find H for the reaction 2H2(g) + 2C(s) + O2(g) the following thermochemical data. C2H5OH (l) + 2 O2 (g) 2 CO2 (g) + 2 H2O (l) C (s) + O2 (g) CO2 (g) H2 (g) + O2 (g) H2O (l)
26-Nov-13 Thermochemistry
3) Find the H for the reaction below, given the following reactions and subsequent H values: PCl5(g) PCl3(g) + Cl2(g) P4(s) + 6Cl2(g) 4PCl3(g) H = -2439 kJ 4PCl5(g) P4(s) + 10Cl 2(g) H = 3438 kJ answer = 249.8 kJ 4) Find the H for the reaction below, given the following reactions and subsequent H values: H2SO4(l) SO3(g) + H2O(g) H2S(g) + 2O2(g) H2SO4(l) H = -235.5 kJ H2S(g) + 2O2(g) SO3(g) + H2O(l) H = -207 kJ H2O(l) H2O(g) H = 44 kJ answer = 72 kJ
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5) Find the H for the reaction below, given the following reactions and subsequent H values: CO2(g) C(s) + O2(g) H2O(l) H2(g) + 1/2O2(g) H = 643 kJ C2H6(g) 2C(s) + 3H 2(g) H = 190.6 kJ 2CO2(g) + 3H2O(l) C 2H6(g) + 7/2O2(g) H = 3511.1 kJ answer = 886 kJ
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Thermochemistry
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