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THERMOCHEMISTRY

Engr. NORMAN GIOVANNI M. GUEVARRA

Energy

Makes objects move


Makes things stop

Energy from sun


eat

plants

foods we

energy to live

We need energy to do work


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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)
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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.

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Heat

Energy that is transferred between objects that have a temperature difference

Engr. NORMAN GIOVANNI M. GUEVARRA

The main form of energy in chemistry is HEAT!

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Energy that flows from something


warm to something cooler

A hotter substance gives KE to a


cooler one

When heat is transferred (lost or


gained), there is a change in the energy within the substance
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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
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System and Surroundings.

System - portion of the universe under study Surrounding - everything else

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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

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Example

You place 10.0g of LiOH in a Styrofoam cup of water. What is the system, and what are the surroundings?

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Internal Energy (U)

Internal energy (U) is the total energy


contained within a system

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Internal Energy (U)

Part of U is kinetic energy (from molecular motion)

Translational motion, rotational motion, vibrational motion. Collectively, these are sometimes called thermal

energy

Part of U is potential energy


Intermolecular and intramolecular forces of attraction, locations of atoms and of bonds. Collectively these are sometimes called chemical

energy

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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.

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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).

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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.
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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?

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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.

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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).

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Law of Conservation of Energy

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.

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First Law of Thermodynamics

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
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First Law: Sign Conventions

Energy entering a system carries a positive sign:


heat absorbed by the system, or work done on the system

Energy leaving a system carries a negative sign

heat given off by the system work done by the system


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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.

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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?

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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?

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Heats of Reaction (qrxn)

qrxn is the quantity of heat

exchanged between a reaction system and its surroundings.

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Exothermic and Endothermic

An exothermic reaction gives off heat

An endothermic reaction absorbs heat

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.
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Conceptualizing an Exothermic Reaction


Surroundings are at 25 C
Typical situation: some heat is released to the surroundings, some heat is absorbed by the solution.

32.2 C

35.4 C

25 C

Hypothetical situation: all heat is instantly released to the surroundings. Heat = qrxn
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In an isolated system, all heat is absorbed by the solution. Maximum temperature rise.
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Internal Energy Change at Constant Volume


For a system where the reaction is carried out at constant volume, DV = 0 and DU = qV. All the thermal energy produced by conversion from chemical energy is released as heat; no P-V work is done.

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Internal Energy Change at Constant Volume

For a system where the reaction is carried out at constant pressure, DU = qP P D V or


DU + P D V = qP

Most of the thermal energy is released as heat.


Some work is done to expand the system against the surroundings (push back the atmosphere).
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Enthalpy and Enthalpy Change


Enthalpy is the sum of
the internal energy and the pressurevolume product of a system:
The evolved H2 pushes back the atmosphere; work is done at constant pressure.

H = U + PV
For a process carried out at constant pressure, qP = DU + PDV so qP = DH
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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.
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Properties of Enthalpy

Enthalpy is an extensive property.

It depends on how much of the substance is present.

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 ____.

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Enthalpy Diagrams

Values of DH are measured experimentally. Negative values indicate exothermic reactions. Positive values indicate endothermic reactions.

A decrease in enthalpy during the reaction; DH is negative.


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An increase in enthalpy during the reaction; DH is positive.


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Reversing Reactions

DH changes sign when a process is reversed. Therefore, a cyclic process has the value DH = 0.
Same magnitude; different signs.

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Thermochemical Reactions

Consists of a chemical equation together with the value of H value that corresponds to the equation when used in molar quantities

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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

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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.

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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
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184.6 kJ

1 mol Cl2
Engr. NORMAN GIOVANNI M. GUEVARRA

184.6 kJ

184.6 kJ

2 mol HCl
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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

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Calorimetry and Calorimeter

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.

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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.

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Calorimetry, Heat Capacity, Specific Heat

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.

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Calorimetry, Heat Capacity, Specific Heat

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
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Heat Capacity: A Thought Experiment

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.

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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.

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More on Specific Heat


q = mass x specific heat x DT

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

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Many metals have low specific heats.

The specific heat of water is higher than that of almost any other substance.

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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?

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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.

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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.

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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.

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Measuring Enthalpy Changes for Chemical Reactions


For a reaction carried out in a calorimeter, the heat evolved by a reaction is absorbed by the calorimeter and its contents.
qrxn = qcalorimeter qcalorimeter = mass x specific heat x DT

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.
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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.

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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 = ?

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Bomb Calorimetry: Reactions at Constant Volume

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.
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Hesss Law of Constant Heat Summation

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

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Hesss Law of Constant Heat Summation

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.
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Hesss Law: An Enthalpy Diagram


We can find DH(a) by subtracting DH(b) from DH(c)

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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.
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DH = 285.8
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Standard Enthalpies of Formation


It would be convenient to be able to use the simple relationship H = Hproducts Hreactants to determine enthalpy changes. Although we dont know absolute values of enthalpy, we dont need them; we can use a relative scale.

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Standard Enthalpy of Formation


When we say The standard enthalpy of formation of CH3OH(l) is 238.7 kJ, we are saying that the reaction:
C(graphite) + 2 H2(g) + O2(g) CH3OH(l)

has a value of H of 238.7 kJ.


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Calculations Based on Standard Enthalpies of Formation


DHrxn = Snp x DHf(products) Snr x DHf(reactants) The symbol S signifies the summation of several terms. The symbol n signifies the stoichiometric coefficient used in front of a chemical symbol or formula. In other words 1. Add all of the values for DHf of the products. 2. Add all of the values for DHf of the reactants. 3. Subtract #2 from #1 (This is usually much easier than using Hesss Law!)
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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.

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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.

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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).

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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.

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Sample Problem 5
Calculate the standard heat of formation of propane using the following data C3H8 + 5O2 3CO2 + 4H2O DH = -530,610 cal

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Ionic Reactions in Solution

We can apply thermochemical concepts to reactions in ionic solution by arbitrarily assigning an enthalpy of formation of zero to H+(aq).

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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).

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The Second Law of Thermodynamics

It is impossible to construct an engine operating in cycles, that absorbs heat at a constant T0 and completely converts it to work.

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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
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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.

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Sample Problem 2
An engine operating at 95% efficiency and temperature of 101oC, calculate T1.

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Entropy (S)

It is a measure of the disorder or randomness of a system.

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Entropy and the Second Law of Thermodynamics


All the spontaneous reactions occur to the second law: the entropy of the universe is steadily increasing. DSsys + DSsurr > 0 DGsys < 0 where: DG = DH TDS

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Sample Problem 1
Formation of sulfuric acid will undergo the following reaction:
SO3 (g) + H2O (l) H2SO4 (l)

What is the standard entropy change?


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Sample Problem 2
Solve for DH, DSo, DGo:
Ba2+ (aq) + CO32- (aq) BaCO3 (s)

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Heats of Formation (25oC)


Substance
AgCl (s) BaCO3 (s) BaSO4 (s) CaCl2 (s) CaSO4 (s) CCl4 (l) CH4 (g) CHCl3 (l) CH3OH (l) CO2 (g) C2H5OH (l) HBr (g) HCl (g) HF (g) HNO3 (l)

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
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-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

Heats of Formation (25oC)


Cation (aq) Ag+ Ba2+ Fe2+ Fe3+ H+ K+ Li+ Mg2+ NH4+ Pb2+ DH0f (KJ/mol) +105.9 -538.4 -87.9 -47.7 0.0 -251.2 -278.5 -462.0 -132.8 +1.6 Anion (aq) Br Cl CO23HCO22MNO4 NO3OHCO43SO42Zn2+ DH0f (KJ/mol) -120.9 167.4 -676.3 691.1 -518.4 -206.6 -229.9 -1284.1 -907.5 -152.4

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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).
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