Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Energy
plants
foods we
energy to live
Energy
Energy is the capacity to do work (to displace or move matter). Energy literally means work within; however, an object does not contain work. Potential energy is energy of position or composition. Kinetic energy is the energy of motion.
Energy has the units of joules (J or kg . m2/s2)
Engr. NORMAN GIOVANNI M. GUEVARRA 3
Ek = mv2
Energy
In chemistry, energy is stored in chemical bonds. When bonds are made, energy is released. When bonds are broken, energy is absorbed.
Heat
Thermochemistry
Study of the heat changes that occur during a chemical reaction The study of the quantity of heat absorbed or given off by chemical reactions. It is a part of Thermodynamics dealing with energy changes associated with physical and chemical reactions
Engr. NORMAN GIOVANNI M. GUEVARRA 8
Type of Systems
Open System - can exchange energy and matter through boundary Close System - can exchange energy through boundary Isolated System - can exchange neither with surroundings
10
Example
You place 10.0g of LiOH in a Styrofoam cup of water. What is the system, and what are the surroundings?
11
12
Translational motion, rotational motion, vibrational motion. Collectively, these are sometimes called thermal
energy
energy
13
Heat (q)
Technically speaking, heat is not energy. Heat is energy transfer between a system and its surroundings, caused by a temperature difference.
Thermal equilibrium occurs when the system and surroundings reach the same temperature and heat transfer stops.
14
Work (w)
Like heat, work is an energy transfer between a system and its surroundings. Unlike heat, work is caused by a force moving through a distance (heat is caused by a temperature difference).
15
Work (w)
A negative quantity of work signifies that the system loses energy. A positive quantity of work signifies that the system gains energy. There is no such thing as negative energy nor positive energy; the sign of work (or heat) signifies the direction of energy flow.
Engr. NORMAN GIOVANNI M. GUEVARRA 16
Pressure-Volume Work
For now we will consider only pressure-volume work. work (w) = PDV
How would the magnitude of DV compare to the original gas volume if the two weights (initial and final) were identical?
17
State
The state of a system: its exact condition at a fixed instant. State is determined by the kinds and amounts of matter present, the structure of this matter at the molecular level, and the prevailing pressure and temperature.
18
State Function
A state function is a property that has a unique value that depends only the present state of a system, and does not depend on how the state was reached (does not depend on the history of the system).
19
Law of Conservation of Energy in a physical or chemical change, energy can be exchanged between a system and its surroundings, but no energy can be created or destroyed.
20
Energy cannot be created or destroyed. Inference: the internal energy change of a system is simply the difference between its final and initial states: DU = Ufinal Uinitial
Additional inference: if energy change occurs only as heat (q) and/or work (w), then: DU = q + w
Engr. NORMAN GIOVANNI M. GUEVARRA 21
Sample Problem 1
If 200 Kcal of heat is absorbed by a system and 50 Kcal or work is done on the surroundings, calculate the change in energy.
23
Sample Problem 2
A gas does 135 J of work while expanding, and at the same time it absorbs 156 J of heat. What is the change in internal energy?
24
Conceptual Example
The internal energy of a fixed quantity of an ideal gas depends only on its temperature. If a sample of an ideal gas is allowed to expand against a constant pressure at a constant temperature, (a) what is DU for the gas? (b) Does the gas do work? (c) Is any heat exchanged with the surroundings?
25
26
In an isolated system, the temperature increases. The system goes from higher to lower energy; qrxn is negative. In an isolated system, the temperature decreases. The system goes from lower to higher energy; qrxn is positive.
Engr. NORMAN GIOVANNI M. GUEVARRA
27
32.2 C
35.4 C
25 C
Hypothetical situation: all heat is instantly released to the surroundings. Heat = qrxn
Prentice Hall 2005
In an isolated system, all heat is absorbed by the solution. Maximum temperature rise.
28
29
H = U + PV
For a process carried out at constant pressure, qP = DU + PDV so qP = DH
Prentice Hall 2005
Mg + 2 HCl MgCl2 + H2
Most reactions occur at constant pressure, so for most reactions, the heat evolved equals the enthalpy change. Engr. NORMAN GIOVANNI M.
GUEVARRA 31
Properties of Enthalpy
Since U, P, and V are all state functions, enthalpy H must be a state function also. Enthalpy changes have unique values. DH = qP
Engr. NORMAN GIOVANNI M. GUEVARRA
Two logs on a fire give off twice as much heat as does one log.
Enthalpy change depends only on the initial and final states. In a chemical reaction we call the initial state the ____ and the final state the ____.
32
Enthalpy Diagrams
Values of DH are measured experimentally. Negative values indicate exothermic reactions. Positive values indicate endothermic reactions.
Reversing Reactions
DH changes sign when a process is reversed. Therefore, a cyclic process has the value DH = 0.
Same magnitude; different signs.
34
Thermochemical Reactions
Consists of a chemical equation together with the value of H value that corresponds to the equation when used in molar quantities
35
Sample Problem 1
Given the equation
(a) H2(g) + I2(s) 2 HI(g) calculate DH for the reaction (b) HI(g) H2(g) + I2(s). DH = +52.96 kJ
36
Sample Problem 2
The complete combustion of liquid octane, C8H18, to produce gaseous carbon dioxide and liquid water at 25 C and at a constant pressure gives off 47.9 kJ of heat per gram of octane. Write a chemical equation to represent this information.
37
H in Stoichiometric Calculations
For problem-solving, heat evolved (exothermic reaction) can be thought of as a product. Heat absorbed (endothermic reaction) can be thought of as a reactant. We can generate conversion factors involving DH. For example, the reaction: H2(g) + Cl2(g) 2 HCl(g) can be used to write: DH = 184.6 kJ
1 mol H2
Prentice Hall 2005
184.6 kJ
1 mol Cl2
Engr. NORMAN GIOVANNI M. GUEVARRA
184.6 kJ
184.6 kJ
2 mol HCl
38
Sample Problem
What is the enthalpy change associated with the formation of 5.67 mol HCl(g) in this reaction? H2(g) + Cl2(g) 2 HCl(g) DH = 184.6 kJ
39
We measure heat flow using calorimetry. A calorimeter is a device used to make this measurement. A coffee cup calorimeter may be used for measuring heat involving solutions.
40
Bomb Calorimeter
A bomb calorimeter is used to find heat of combustion; the bomb contains oxygen and a sample of the material to be burned.
41
Heat evolved in a reaction is absorbed by the calorimeter and its contents. In a calorimeter we measure the temperature change of water or a solution to determine the heat absorbed or evolved by a reaction.
42
The heat capacity (C) of a system is the quantity of heat required to change the temperature of the system by 1 C. C = q/DT (units are J/C) Molar heat capacity is the heat capacity of one mole of a substance. The specific heat (s) is the heat capacity of one gram of a pure substance (or homogeneous mixture). s = C/m = q/(mDT) q = s m DT
Engr. NORMAN GIOVANNI M. GUEVARRA 43
Place an empty iron pot weighing 5 lb on the burner of a stove. Place an iron pot weighing 1 lb and containing 4 lb water on a second identical burner (same total mass). Turn on both burners. Wait five minutes. Which pot handle can you grab with your bare hand? Iron has a lower specific heat than does water. It takes less heat to warm up iron than it does water.
44
Sample Problem
Calculate the heat capacity of an aluminum block that must absorb 629 J of heat from its surroundings in order for its temperature to rise from 22 C to 145 C.
45
If DT is positive (temperature increases), q is positive and heat is gained by the system. If DT is negative (temperature decreases), q is negative and heat is lost by the system. The calorie, while not an SI unit, is still used to some extent. Water has a specific heat of 1 cal/(g oC). 4.184 J = 1 cal One food calorie (Cal or kcal) is actually equal to 1000 cal. Engr. NORMAN GIOVANNI M.
GUEVARRA
46
The specific heat of water is higher than that of almost any other substance.
47
Sample Problem 1
How much heat, in joules and in kilojoules, does it take to raise the temperature of 225 g of water from 25.0 to 100.0 C?
48
Sample Problem 2
What will be the final temperature if a 5.00-g silver ring at 37.0 C gives off 25.0 J of heat to its surroundings? Use the specific heat of silver listed in Table 6.1.
49
Sample Problem 3
A 15.5-g sample of a metal alloy is heated to 98.9 C and then dropped into 25.0 g of water in a calorimeter. The temperature of the water rises from 22.5 to 25.7 C. Calculate the specific heat of the alloy.
50
Sample Problem 4
Without doing detailed calculations, determine which of the following is a likely approximate final temperature when 100 g of iron at 100 C is added to 100 g of 20 C water in a calorimeter: (a) 20 C (b) 30 C (c) 60 C (d) 70 C.
51
By measuring the temperature change that occurs in a calorimeter, and using the specific heat and mass of the contents, the heat evolved (or absorbed) by a reaction can be determined and the enthalpy change calculated.
Prentice Hall 2005 Engr. NORMAN GIOVANNI M. GUEVARRA 52
Sample Problem 1
A 50.0-mL sample of 0.250 M HCl at 19.50 C is added to 50.0 mL of 0.250 M NaOH, also at 19.50 C, in a calorimeter. After mixing, the solution temperature rises to 21.21 C. Calculate the heat of this reaction.
53
Sample Problem 2
Express the result of Sample Problem 2 for molar amounts of the reactants and products. That is, determine the value of DH that should be written in the equation for the neutralization reaction: HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) DH = ?
54
Some reactions, such as combustion, cannot be carried out in a coffee-cup calorimeter. In a bomb calorimeter, a sample of known mass is placed in a heavy-walled bomb, which is then pressurized with oxygen.
Since the reaction is carried out at constant volume, qrxn = qcalorimeter = DU but in many cases the value of DU is a good approximation of DH.
Prentice Hall 2005 Engr. NORMAN GIOVANNI M. GUEVARRA 55
Some reactions cannot be carried out as written. Consider the reaction: C(graphite) + O2(g) CO(g). If we burned 1 mol C in mol O2, both CO and CO2 would probably form. Some C might be left over. However
56
enthalpy change is a state function. The enthalpy change of a reaction is the same whether the reaction is carried out in one step or through a number of steps. Hesss Law: If an equation can be expressed as the sum of two or more other equations, the enthalpy change for the desired equation is the sum of the enthalpy changes of the other equations.
Engr. NORMAN GIOVANNI M. GUEVARRA 57
58
Sample Problem 1
Calculate the enthalpy change for reaction (a) given the data in equations (b), (c), and (d).
(a) 2 C(graphite) + 2 H2(g) C2H4(g) (b) C(graphite) + O2(g) CO2(g) DH = ? DH = 393.5 kJ DH = 1410.9
(c) C2H4(g) + 3 O2 2 CO2(g) + 2 H2O(l) kJ (d) H2(g) + O2 H2O(l) kJ Engr. NORMAN GIOVANNI M.
Prentice Hall 2005 GUEVARRA
DH = 285.8
59
60
61
Sample Problem 1
Synthesis gas is a mixture of carbon monoxide and hydrogen that is used to synthesize a variety of organic compounds. One reaction for producing synthesis gas is 3 CH4(g) + 2 H2O(l) + CO2(g) 4 CO(g) + 8 H2(g) H =? Use standard enthalpies of formation from the Table to calculate the standard enthalpy change for this reaction.
63
Sample Problem 2
The combustion of isopropyl alcohol, common rubbing alcohol, is represented by the equation
2 (CH3)2CHOH(l) + 9 O2(g) 6 CO2(g) + 8 H2O(l) H = 4011 kJ
Use this equation and data from the Table to establish the standard enthalpy of formation for isopropyl alcohol.
64
Sample Problem 3
Without performing a calculation, determine which of these two substances should yield the greater quantity of heat per mole upon complete combustion: ethane, C2H6(g), or ethanol, CH3CH2OH(l).
65
Sample Problem 4
The heat of combustion at constant volume of CH4 is measured in a calorimeter at 25oC is found out be 885.4 KJ/mol. Calculate DH.
66
Sample Problem 5
Calculate the standard heat of formation of propane using the following data C3H8 + 5O2 3CO2 + 4H2O DH = -530,610 cal
67
We can apply thermochemical concepts to reactions in ionic solution by arbitrarily assigning an enthalpy of formation of zero to H+(aq).
68
Sample Problem 1
H+(aq) + OH(aq) H2O(l) 55.8 kJ H =
Use the net ionic equation just given, together with Hf = 0 for H+(aq), to obtain Hf for OH(aq).
69
It is impossible to construct an engine operating in cycles, that absorbs heat at a constant T0 and completely converts it to work.
70
According to Carnot (1796 - 1832) and Lord Kelvin (1824 1907), the maximum efficiency of the engine is: maximum efficiency
(T2 T1) T2
Where T1 T2
= =
low T in K high T in K
Engr. NORMAN GIOVANNI M. GUEVARRA
71
Sample Problem 1
A frictionless, well insulated steam engine is operating between the normal boiling point of water, 100oC and room temperature, 27oC. Calculate the maximum efficiency.
72
Sample Problem 2
An engine operating at 95% efficiency and temperature of 101oC, calculate T1.
73
Entropy (S)
74
Sample Problem 1
Formation of sulfuric acid will undergo the following reaction:
SO3 (g) + H2O (l) H2SO4 (l)
76
Sample Problem 2
Solve for DH, DSo, DGo:
Ba2+ (aq) + CO32- (aq) BaCO3 (s)
77
DH0 (KJ/mol)
Substance
DH0 (KJ/mol)
-241.8 -285.8 -187.6 -811.6 -392.2 -435.9 -641.8 -1113.0 -924.7 -411.0 -569.0 -426.2 -46.2 -315.4 -545.2
78
-127.0 H2 O (g) -1218.8 H2 O (l) -1465.2 H2O2 (l) -795.0 H2SO4 (l) -1432.7 KBr (s) -139.8 KCl (s) -74.3 MgCl2 (s) -131.8 MgCO3 (s) -238.6 Mg(OH)2 (s) -393.5 NaCl (s) -277.6 NaF (s) -36.2 NaOH (s) NH3 (g) -92.3 NH3 (l) -92.3 SnCl4 (l) -173.2 Engr. NORMAN GIOVANNI M.
GUEVARRA
79
Application
Fossil Fuels: Coal, Natural Gas, and Petroleum A fuel is a substance that burns with the release of heat. These fossil fuels were formed over a period of millions of years from organic matter that became buried and compressed under mud and water. Foods: Fuels for the Body The three principal classes of foods are carbohydrates, fats, and proteins. 1 Food Calorie (Cal) is equal to 1000 cal (or 1 kcal).
Engr. NORMAN GIOVANNI M. GUEVARRA 80