This chapter discusses thermochemistry and the concepts of heat, work, internal energy, enthalpy, and the first law of thermodynamics. It introduces terminology like system, surroundings, heat capacity, and heat of reaction. Methods for determining heats of reaction through calorimetry are presented, including bomb calorimetry and coffee cup calorimetry. The relationship between internal energy, enthalpy, and heat of reaction is explored. Standard states and standard enthalpy changes are defined. Hess's law for determining heats of reaction indirectly is introduced.
The Prins-Pinacol reaction is a two step process. It begins with the Prins reaction, which is the attack by a nucleophilic alkene on a Lewis acid-activated aldehyde. This forms a cationic intermediate. The pinacol rearrangement is a methyl shift which pushes the cation on to an oxygen, which is then deprotonated.
Contributed by: Andy Clevenger (Undergraduate), University of Utah, 2016
The Prins-Pinacol reaction is a two step process. It begins with the Prins reaction, which is the attack by a nucleophilic alkene on a Lewis acid-activated aldehyde. This forms a cationic intermediate. The pinacol rearrangement is a methyl shift which pushes the cation on to an oxygen, which is then deprotonated.
Contributed by: Andy Clevenger (Undergraduate), University of Utah, 2016
Chelation Trends and Antibacterial Activity of Some Mixed Ligand ChelatesTaghreed Al-Noor
Synthesis and investigation of new Co(II), Ni(II), Cu(II), Zn(II) and Cr(III)chelates of mixed ligands including
aSchiff base [(E)-2-(4-(dimethylamino)benzylideneamino)phenol] (C15H16N2O) derived from the condensation of 4-
dimethylaminobenzaldehyde with 2-aminophenol as main ligand (L1) and an amino acid; L-Histidine as co-ligand (L2)
were studied. The obtained Schiff base and the mixed ligand chelates were subjected to several physiochemical
techniques, in terms of CHN elemental analyses, molar conductivity, magnetic moment measurements, infrared,
electronic and mass spectroscopies. The CHN analytical data showed the formation of the Schiff base compound and the
mixed ligand chelates in 1:1:1[M:L1:L2] ratio. All the prepared mixed ligand chelates were non-electrolyte in nature.
The infrared spectral data exhibited that the used ligands behaving as bidentate ligands towards the metal ions. The
1HNMR spectra of the ligands and their Zn(II) mixed ligand chelate exhibited the effect of the activated groups of the
ligands by the metal ion. The electronic spectral results showed the existence of π→π* (phenyl ring) and n→π*(HC=N)
and suggested the geometrical structures of the chelates. Meanwhile, the mass spectral data revealed the fragmentations
of the Schiff base, Histidine and their Cu(II) mixed ligand chelate. The studies made on these chelates proposed a six
coordinated octahedral geometry for all these chelates. The antibacterial activities of the Schiff base, Histidine, metal
salts and mixed ligand chelates were screened. It is found that the mixed ligand chelates have the most biological activity
in comparison to the free ligands and salts.
Keywords: Schiff base; 4-dimethylaminobenzaldehyde; 2-aminophenol; Histidine; mixed ligand chelates;
Physiochemical techniques; Antibacterial activity.
Need of thermodynamics and the Laws of Thermodynamics.
Important principles and definitions of thermochemistry.
Concept of standard state and standard enthalpies of formations,
Integral and differential enthalpies of solution and dilution.
Calculation of bond energy, bond dissociation energy and resonance energy from thermochemical data.
Variation of enthalpy of a reaction with temperature – Kirchhoff’s equation.
Statement of Third Law of thermodynamics and calculation of absolute entropies of substances.
JFI -just for information
Honour Chemistry Unit 4: Thermochemistry and Nuclear Chemistry
Copyrighted by Gabriel Tang B.Ed., B.Sc. Page 135.
Unit 4: THERMOCHEMISTRY AND NUCLEAR CHEMISTRY
Chapter 6: Thermochemistry
6.1: The Nature of Energy and Types of Energy
Energy (E): - the ability to do work or produce heat.
Different Types of Energy:
1. Radiant Energy: - solar energy from the sun.
2. Thermal Energy: - energy associated with the random motion of atoms and molecules.
3. Chemical Energy: - sometimes refer to as Chemical Potential Energy. It is the energy stored in the
chemical bonds, and release during chemical change.
4. Potential Energy: - energy of an object due to its position.
First Law of Thermodynamics: - states that energy cannot be created or destroyed. It can only be
converted from one form to another. Therefore, energy in the universe is
a constant.
- also known as the Law of Conservation of Energy (ΣEinitial = ΣEfinal).
6.2: Energy Changes in Chemical Reactions
Heat (q): - the transfer of energy between two objects (internal versus surroundings) due to the difference
in temperature.
Work (w): - when force is applied over a displacement in the same direction (w = F × d).
- work performed can be equated to energy if no heat is produced (E = w). This is known as the
Work Energy Theorem.
System: - a part of the entire universe as defined by the problem.
Surrounding: - the part of the universe outside the defined system.
Open System: - a system where mass and energy can interchange freely with its surrounding.
Closed System: - a system where only energy can interchange freely with its surrounding but mass not
allowed to enter or escaped the system.
Isolated System: - a system mass and energy cannot interchange freely with its surrounding.
Unit 4: Thermochemistry and Nuclear Chemistry Honour Chemistry
Page 136. Copyrighted by Gabriel Tang B.Ed., B.Sc.
Exothermic Process (ΔE < 0): - when energy flows “out” of the system into the surrounding.
(Surrounding gets Warmer.)
Endothermic Process (ΔE > 0): - when energy flows into the system from the surrounding.
(Surrounding gets Colder.)
6.3: Introduction of Thermodynamics
Thermodynamics: - the study of the inter action of heat and other kinds of energy.
State of a System: - the values of all relevant macroscopic properties like composition, energy,
temperature, pressure and volume.
State Function: - also refer to as State Property of a system at its present conditions.
- energy is a state function because of its independence of pathway, whereas work and heat
are not state properties.
Pathway: - the specific conditions that dictates ...
2. Contents
7-1 Getting Started: Some Terminology
7-2 Heat
7-3 Heats of Reaction and Calorimetry
7-4 Work
7-5 The First Law of Thermodynamics
7-6 Heats of Reaction: ∆U and ∆H
7-7 The Indirect Determination of ∆H: Hess’s Law
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3. Contents
7-7 The Indirect Determination of ∆H, Hess’s Law
7-8 Standard Enthalpies of Formation
7-9 Fuels as Sources of Energy
Focus on Fats, Carbohydrates, and Energy
Storage
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4. 6-1 Getting Started: Some Terminology
• System
• Surroundings
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5. Terminology
• Energy, U
– The capacity to do work.
• Work
– Force acting through a distance.
• Kinetic Energy
– The energy of motion.
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6. Energy
• Kinetic Energy
1 kg m2
ek = mv2 [ek ] = 2 = J
2 s
• Work
kg m m
w = Fd [w ] = = J
s 2
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7. Energy
• Potential Energy
– Energy due to condition, position, or
composition.
– Associated with forces of attraction or
repulsion between objects.
• Energy can change from potential to
kinetic.
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8. Energy and Temperature
• Thermal Energy
– Kinetic energy associated with random
molecular motion.
– In general proportional to temperature.
– An intensive property.
• Heat and Work
– q and w.
– Energy changes.
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9. Heat
Energy transferred between a system and its
surroundings as a result of a temperature
difference.
• Heat flows from hotter to colder.
– Temperature may change.
– Phase may change (an isothermal process).
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10. Units of Heat
• Calorie (cal)
– The quantity of heat required to change the
temperature of one gram of water by one degree
Celsius.
• Joule (J)
– SI unit for heat
1 cal = 4.184 J
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11. Heat Capacity
• The quantity of heat required to change the
temperature of a system by one degree.
– Molar heat capacity.
• System is one mole of substance.
– Specific heat capacity, c. q = mc∆T
• System is one gram of substance
– Heat capacity q = C∆T
• Mass specific heat.
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12. Conservation of Energy
• In interactions between a system and its
surroundings the total energy remains constant—
energy is neither created nor destroyed.
qsystem + qsurroundings = 0
qsystem = -qsurroundings
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14. Example 7-2
Determining Specific Heat from Experimental Data.
Use the data presented on the last slide to calculate the specific
heat of lead.
qlead = -qwater
qwater = mc∆T = (50.0 g)(4.184 J/g °C)(28.8 - 22.0)°C
qwater = 1.4x103 J
qlead = -1.4x103 J = mc∆T = (150.0 g)(c)(28.8 - 100.0)°C
clead = 0.13 Jg-1°C-1
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15. 7-3 Heats of Reaction and Calorimetry
• Chemical energy.
– Contributes to the internal energy of a system.
• Heat of reaction, qrxn.
– The quantity of heat exchanged between a
system and its surroundings when a chemical
reaction occurs within the system, at constant
temperature.
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16. Heats of Reaction
• Exothermic reactions.
– Produces heat, qrxn < 0.
• Endothermic reactions.
– Consumes heat, qrxn > 0.
• Calorimeter
– A device for measuring quantities of heat.
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17. Bomb Calorimeter
qrxn = -qcal
qcal = qbomb + qwater + qwires +…
Define the heat capacity of the
calorimeter:
heat
qcal = mici∆T = C∆T
all i
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18. Example 7-3
Using Bomb Calorimetry Data to Determine a Heat of Reaction.
The combustion of 1.010 g sucrose, in a bomb calorimeter,
causes the temperature to rise from 24.92 to 28.33°C. The
heat capacity of the calorimeter assembly is 4.90 kJ/°C.
(a) What is the heat of combustion of sucrose, expressed in
kJ/mol C12H22O11
(b) Verify the claim of sugar producers that one teaspoon of
sugar (about 4.8 g) contains only 19 calories.
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19. Example 7-3
Calculate qcalorimeter:
qcal = C∆T = (4.90 kJ/°C)(28.33-24.92)°C = (4.90)(3.41) kJ
= 16.7 kJ
Calculate qrxn:
qrxn = -qcal = -16.7 kJ per 1.010 g
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20. Example 7-3
Calculate qrxn in the required units:
-16.7 kJ
qrxn = -qcal = = -16.5 kJ/g
1.010 g
343.3 g
qrxn = -16.5 kJ/g
1.00 mol
= -5.65 103 kJ/mol (a)
Calculate qrxn for one teaspoon:
4.8 g 1.00 cal
qrxn = (-16.5 kJ/g)( )( )= -19 cal/tsp (b)
1 tsp 4.184 J
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21. Coffee Cup Calorimeter
• A simple calorimeter.
– Well insulated and therefore isolated.
– Measure temperature change.
qrxn = -qcal
See example 7-4 for a sample calculation.
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22. 7-4 Work
• In addition to heat effects chemical reactions
may also do work.
• Gas formed pushes against
the atmosphere.
• Volume changes.
• Pressure-volume work.
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23. Pressure Volume Work
w=Fd
= (P A) h
= P∆V
w = -Pext∆V
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24. Example 7-5
7-3
Calculating Pressure-Volume Work.
Suppose the gas in the previous figure is 0.100 mol He at 298 K.
How much work, in Joules, is associated with its expansion at
constant pressure.
Assume an ideal gas and calculate the volume change:
Vi = nRT/P
= (0.100 mol)(0.08201 L atm mol-1 K-1)(298K)/(2.40 atm)
= 1.02 L
∆V = 1.88-1.02 L = 0.86 L
Vf = 1.88 L
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25. Example 7-5
7-3
Calculate the work done by the system:
w = -P∆V Hint: If you use
101 J pressure in kPa you
= -(1.30 atm)(0.86 L)( )
1 L atm get Joules directly.
= -1.1 102 J
Where did the conversion factor come from?
Compare two versions of the gas constant and calculate.
8.3145 J/mol K ≡ 0.082057 L atm/mol K
1 ≡ 101.33 J/L atm
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26. 7-5 The First Law of Thermodynamics
• Internal Energy, U.
– Total energy (potential and kinetic) in a system.
•Translational kinetic energy.
•Molecular rotation.
•Bond vibration.
•Intermolecular attractions.
•Chemical bonds.
•Electrons.
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27. First Law of Thermodynamics
• A system contains only internal energy.
– A system does not contain heat or work.
– These only occur during a change in the system.
∆U = q + w
• Law of Conservation of Energy
– The energy of an isolated system is constant
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28. First Law of Thermodynamics
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29. State Functions
• Any property that has a unique value for a
specified state of a system is said to be a
State Function.
• Water at 293.15 K and 1.00 atm is in a specified state.
• d = 0.99820 g/mL
• This density is a unique function of the state.
• It does not matter how the state was established.
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30. Functions of State
• U is a function of state.
– Not easily measured.
∀ ∆U has a unique value between two states.
– Is easily measured.
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31. Path Dependent Functions
• Changes in heat and work are not functions of
state.
– Remember example 7-5, w = -1.1 102 J in a one step
expansion of gas:
– Consider 2.40 atm to 1.80 atm and finally to 1.30 atm.
w = (-1.80 atm)(1.30-1.02)L – (1.30 atm)(1.88-1.36)L
= -0.61 L atm – 0.68 L atm = -1.3 L atm
= 1.3 102 J
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32. 7-6 Heats of Reaction: ∆U and ∆H
Reactants → Products
Ui Uf
∆U = Uf - Ui
∆U = qrxn + w
In a system at constant volume:
∆U = qrxn + 0 = qrxn = qv
But we live in a constant pressure world!
How does qp relate to qv?
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34. Heats of Reaction
qV = qP + w
We know that w = - P∆V and ∆U = qP, therefore:
∆U = qP - P∆V
qP = ∆U + P∆V
These are all state functions, so define a new function.
Let H = U + PV
Then ∆H = Hf – Hi = ∆U + ∆PV
If we work at constant pressure and temperature:
∆H = ∆U + P∆V = qP
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36. Changes of State of Matter
Molar enthalpy of vaporization:
H2O (l) → H2O(g) ∆H = 44.0 kJ at 298 K
Molar enthalpy of fusion:
H2O (s) → H2O(l) ∆H = 6.01 kJ at 273.15 K
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37. Example 7-8
7-3
Enthalpy Changes Accompanying Changes in States of Matter.
Calculate ∆H for the process in which 50.0 g of water is
converted from liquid at 10.0°C to vapor at 25.0°C.
Break the problem into two steps: Raise the temperature of
the liquid first then completely vaporize it. The total enthalpy
change is the sum of the changes in each step.
Set up the equation and calculate:
qP = mcH2O∆T + n∆Hvap
50.0 g
= (50.0 g)(4.184 J/g °C)(25.0-10.0)°C + 44.0 kJ/mol
18.0 g/mol
= 3.14 kJ + 122 kJ = 125 kJ
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38. Standard States and Standard Enthalpy
Changes
• Define a particular state as a standard state.
• Standard enthalpy of reaction, ∆H°
– The enthalpy change of a reaction in which all
reactants and products are in their standard states.
• Standard State
– The pure element or compound at a pressure of 1
bar and at the temperature of interest.
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40. 7-7 Indirect Determination of ∆H:
Hess’s Law
∀ ∆H is an extensive property.
– Enthalpy change is directly proportional to the amount of
substance in a system.
N2(g) + O2(g) → 2 NO(g) ∆H = +180.50 kJ
½N2(g) + ½O2(g) → NO(g) ∆H = +90.25 kJ
∀ ∆H changes sign when a process is reversed
NO(g) → ½N2(g) + ½O2(g) ∆H = -90.25 kJ
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41. Hess’s Law
• Hess’s law of constant heat summation
– If a process occurs in stages or steps (even hypothetically),
the enthalpy change for the overall process is the sum of the
enthalpy changes for the individual steps.
½N2(g) + ½O2(g) → NO(g) ∆H = +90.25 kJ
NO(g) + ½O2(g) → NO2(g) ∆H = -57.07 kJ
½N2(g) + O2(g) → NO2(g) ∆H = +33.18 kJ
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43. 7-8 Standard Enthalpies of Formation
∆Hf°
• The enthalpy change that occurs in the
formation of one mole of a substance in the
standard state from the reference forms of
the elements in their standard states.
• The standard enthalpy of formation of a
pure element in its reference state is 0.
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44. Standard Enthalpies of Formation
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45. Standard Enthalpies of Formation
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46. Standard Enthalpies of Reaction
∆Hoverall = -2∆Hf°NaHCO3+ ∆Hf°Na2CO3
+ ∆Hf°CO2 + ∆Hf°H2O
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47. Enthalpy of Reaction
∆Hrxn = ∆Hf°products- ∆Hf°reactants
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48. Table 7.3 Enthalpies of Formation of Ions
in Aqueous Solutions
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49. 7-9 Fuels as Sources
of Energy
• Fossil fuels.
– Combustion is exothermic.
– Non-renewable resource.
– Environmental impact.
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Thermochemistry branch of chemistry concerned with heat effects accompanying chemical reactions. Direct and indirect measurement of heat. Answer practical questions: why is natural gas a better fuel than coal, and why do fats have higher energy value than carbohydrates and protiens.
Energy is from the Greek “work within”. Moving objects do work when they slow down or are stopped. Kinetic means “motion” in greek.
[w] means UNITS OF WORK, not concentration in this case.
Energy changes continuously from potential to kinetic. Energy is lost to the surroundings.
Heat is transfer of energy. Bodies do NOT contain heat.
In practice, the temperature is allowed to change and the heat that is lost or needed as the system returns to its original temperature is calculated.
Heat of reaction in an isolated system produces a change in the thermal energy of the system. The causes a temperature change. In an non-isolated system the temperature remains constant and the heat is transferred to the surroundings. Top picture is CaO(s) + H 2 O(l) → Ca(OH) 2 Bottome picture is Ba(OH) 2 ·8H 2 O + 2NH 4 Cl(s)→BaCl 2 (s) + 2 NH 3 (aq) + 8 H 2 O(l)
System includes everything inside the double walled container. All the water, wires, stirrer, thermometer, and the reaction chamber. Bomb is filled with sample and assembled. Then pressurized witih O 2 . A short pulse of electric current heats the sample and ignites it. The final temperature of the calorimeter assembly is determined after the combustion reaction. Because the reaction is carried out at a fixed volume we say that this is at constant volume.
Negative sign is introduced for P ext because the system does work ON the surroundings. When a gas expands V is positive and w is negative. When a gas is compressed V is negative and w is positive, indicating that energy (as work) enters the system. In many cases the external pressure is the same as the internal pressure of the system, so P ext is often just represented as P
Note that this conversion factor is simply kPa/atm.
Temperature must be specified because H varies with temperature.
Absolute enthalpy cannot be determined. H is a state function so changes in enthalpy, H, have unique values. Reference forms of the elements in their standard states are the most stable form of the element at one bar and the given temperature. The superscript degree symbol denotes that the enthalpy change is a standard enthalpy change and The subscript “f” signifies that the reaction is one in which a substance is formed from its elements.