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ENERGY AND ITS DIFFERENT FORMS

What is Energy - good question! - capacity to do work or to supply heat - best to learn what is energy through examples Kinetic and Potential Energy Kinetic Energy - energy of movement - K.E. = mv2 m mass v velocity - examples - baseball moving - thermal energy (molecules moving) Potential Energy - energy stored that is released through motion - examples - ball in air

Potential energy depends on distance from earths surface.

- battery - electrical energy is stored in battery - electrons start moving when circuit is made - thus electrical energy is released - chemical energy - Potential chemical energy of wood is changed into kinetic energy when it is burned. - Explosives have a large amount of potential energy. TYPES OF ENERGY Light Energy as in energy from a light bulb Heat Energy as in energy from a fire Electrical Energy as in putting your finger in an electrical socket Ouch! Mechanical Energy as in energy from an engine or water wheel Chemical Energy as in energy from burning gasoline (chemical energy is converted to heat and light) - Chemical energy is stored inside a substance until a substance undergoes a chemical change. Then it can released or sometimes absorbed. **- Chemical energy is stored in chemical bonds between atoms.**

Energy exchange in chemical reactions Exothermic - energy is released when reaction occurs - most reactions are exothermic Endothermic - energy is absorbed when reaction occurs - example is an instant cold pack. Potential energy can be converted to kinetic energy. - ball falling - log burning - discharging battery Kinetic energy can be converted to potential energy - lifting box - charging battery - electricity is generated by motion - waterfall, windmill, steam turbine, etc Definition: Internal Energy is the sum of kinetic and potential energy in a thermodynamic system. Types of internal energy 1. Translational - Particle moves in a straight line, i. e., particle is translated. - Only can be kinetic energy. 2. Vibrational - Atoms in a bond vibrate as if on a spring. - Springs can have potential and kinetic energy. Example: vibrations of water
H O O H H H H H O H H O

symmetric stretch
H O H H H

antisymmetric stretch

O bending 3. Rotational - Molecule rotates on axis - Rotational energy can only be kinetic energy.

4. Electronic - Arrangement of electrons (and nuclei) is major contribution to the potential energy of a molecule. - Kinetic energy is also important. - Kinetic energy is always related to potential energy when objects are bound together.

STATE FUNCTIONS
- A State Function is a thermodynamic quantity whose value depends only on the state at the moment, i. e., the temperature, pressure, volume, etc - The value of a state function is independent of the history of the system. - Internal energy is an example of a state function. - The fact that internal energy is a state function is extremely useful because it we can measure the energy change in the system by knowing the initial energy and the final energy. - In other words, we dont need all of the nitty-gritty detail of a process to measure the change in the value of a state function. - In contrast, we do need all of the nitty-gritty details to measure the heat or the work of a system.

ENERGY UNITS
Joule

kg m2 defined as 1J = 1 2 s
1 m2 kg m2 2 K. E. = mv kg 2 = 2 s s2 - SI unit (our preferred unit)

Calorie - 1 cal = 4.184 J (exact) (new definition of cal.) - old definition of calorie: energy needed to raise the temperature of 1 g of H2O 1 C - aside: 1 dietary calorie = 1 Cal = 1 kcal

SYSTEM AND SURROUNDINGS

For a thermodynamic process, the universe can be broken into two parts. 1.) System contains what were interested in 2.) Surroundings everything else Example: For a beaker of melting ice System beaker and ice Surroundings laboratory and everything else Example: Measuring the heat of neutralization in a coffee cup calorimeter System reaction e.g. NaOH + HCl Surroundings water and calorimeter or System reaction, water and calorimeter Surroundings laboratory *Defining system and surroundings is a matter of perspective.* example of an isolated system

HEAT AND WORK

Two ways to classify conversion of potential energy to kinetic energy and vice versa. Heat q - chaotic change in molecular motion - related to temperature - heating increases (or decreases) molecular motion in all directions Work w - concerted change in molecular motion - Work = Force distance w = F d - movement against force is work - work increases (or decreases) molecular motion in a specific direction - in gases, work is related to changes in volume *Heat and work are not state functions.* Sign Convention heat +q = heat gained by system - q = heat lost by system work +w = work done on system - w = work done by system

(compression) (expansion)

THE FIRST LAW OF THERMODYNAMICS

A change in the internal energy of a system is due only heat and work. E = q + w - Energy is gained or lost depending how heat is gained or lost and how work is done. - Calculate change in energy by adding heat and work - In other words, the sum of the kinetic energy change and the potential energy change of a system is equal to the heat and the work. Remarkable!! Example: If a process emits 33 kJ of heat and does 28 kJ of work, what is the total change of energy? Emit 33 kJ of heat 28 kJ of work done q = -33 kJ w = -28 kJ

E = q + w = -33kJ - 28 kJ = -61 kJ In other words, overall the system lost 61 kJ of energy.

ENTHALPY H
- modified form of internal energy - state function - value is very close to value of internal energy for most chemical systems. Changes in Enthalpy **- Change in enthalpy for constant pressure process is equivalent to heat.** H = Hf Hi = qp - Sign convention for enthalpy is same as sign convention for heat. - If enthalpy is constant pressure heat, then why not just use heat? - Enthalpy is state function, heat is not. - At constant pressure, enthalpy happens to be equal to heat. Enthalpies of Formation Hf - heat evolved or absorbed when substance is formed from elements - review definition of formation reaction - experimentally measured quantity - values found in thermodynamic tables - such as Appendix C in Brown LeMay and Bursten - by definition, elements have zero enthalpy of formation - Hf(Fe) = 0; Hf(O2) = 0; Hf(P4) = 0 Example 2 C(s) + 3 H2 (g) + O2 (g) C2H5OH (l) Hf(C2H5OH (l)) = - 277 kJ/mol Na (s) + Cl2 (g) NaCl (s) Hf(NaCl (s)) = - 410.9 kJ/mol *Phase of compound is important.* Hf(H2O (g)) Hf(H2O (l)) Hf(H2O (g)) = - 241.82 kJ/mol Hf(H2O (l)) = - 285.83 kJ/mol Enthalpy of Reaction Hrxn - From balanced equation, add enthalpies of products and subtract enthalpies of reactants. Hrxn = Hf (products) - Hf (reactants) - symbol meaning summation

Example: Calculate the enthalpy of reaction for the combustion of ethanol. C2H5OH (l) + 3 O2 (g) 2 CO2 (g) + 3 H2O (g) Hrxn = 2 x Hf(CO2) + 3 x Hf(H2O) Hf(C2H5OH) 3 x Hf (O2) At this point, we need to find Hf of components in thermodynamic table.

Example: Calculate the enthalpy of reaction for the hydration of phosphoric acid anhydride. P2O5 (s) + 3 H2O (l) 2 H3PO4 (aq)

Again, we need to find Hf in a thermodynamic table. Hrxn = 2(-1288.3 kJ/mol) (-1470.1 kJ/mol) 3(-285.83 kJ/mol) = -249.0 kJ/mol Note we had to be careful about the phase of H2O. Example: Calculate the enthalpy of neutralization of NaOH with HCl. NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq) Hrxn = Hf(NaCl) + Hf(H2O) Hf (NaOH) Hf(HCl)

Note being careful about the phases of components. Properties of Enthalpy 1. Enthalpy is an extensive property - i.e., value depends on amount of substance 2. Molar enthalpy is an intensive property!! Hrxn = -56.1 kJ/mol 1 mol NaOH + 1 mol HCl Hrxn = -56.1 kJ 2 mol NaOH + 2 mol HCl Hrxn = -112.2 kJ 3.47 mol NaOH + 3.47 mol HCl

Example: Calculate the heat emitted when 753 g of propane, C3H8 is combusted. C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l) Hrxn = -2220 kJ/molrxn moles of C3H8 heat emitted

**CAUTION: Point of Confusion** - When enthalpy of reaction is stated as kJ/mol, what is meant is kJ/molrxn. - There is often more than one mole of substance per reaction mole. Example: Calculate the heat emitted when 8.7 mol of CO is combusted. 2 CO (g) + O2 (g) 2 CO2 (g) Hrxn = -566.0 kJ/mol

Example: Calculate the heat emitted when 8.7 mol of CO is combusted. CO (g) + O2 (g) CO2 (g) Hrxn = -283.0 kJ/mol

Properties of Enthalpy cont 3. Enthalpy of reverse reaction is same value with sign changed. P4 (s) + 6 Cl2 (g) 4 PCl3 (l) Reverse reaction 4 PCl3 (l) P4 (s) + 6 Cl2 (g) Hrxn = -1279 kJ/mol Hrxn = +1279 kJ/mol

CALORIMETRY
- literally: heat measuring - experimentally determine Hrxn with calorimeter - constant pressure calorimeter - coffee cup calorimeter - enthalpy change occurs at atmospheric pressure - constant volume calorimeter - bomb calorimeter - enthalpy change occurs in a sealed container with constant volume - general principle of calorimetry Heat Lost = - Heat Gained - This is a restatement of conservation of energy.

Quantifying heat - heat of substance is proportional to both mass and temperature difference - Heat equation q = m c T q heat m mass T = Tf Ti c proportionality constant

- proportionality constant is called specific heat - The specific heat quantifies how much heat is needed to raise (or lower) temperature of substance. - Compare specific heats of Cu and H2O. - c(Cu) = 0.3866 J/g C - c(H2O) = 4.184 J/g C - copper heats and cools quicker - water heats and cools slower Example: How much heat is lost when 3780 g of H2O (1 gallon) is cooled from 61.4 C to 30.0 C?

Example: A copper-bottomed saucepan has a heat capacity of 227.3 J/C. Calculate how much heat the saucepan gains when its temperature changes from 24.7 C to 110.2 C. Aside: The mass and the specific heat of an object are often combined into a single quantity known as the heat capacity, C. The heat equation written in terms of the heat capacity is q = [m c] T = C T. q = C T = 227.3 J/C (110.2 C 24.7 C) = 19.4 kJ

Note sign of heat: Positive heat means heat is absorbed. Also note: The relative values of the heats calculated in two previous examples. Since water has a higher specific heat than iron and copper, even lukewarm water has more heat than a hot pan. Example: 13.2 g of KOH (s) is added to 100 mL of H2O. The temperature of the solution changes from 23.1 C to 54.2 C. Assume the density of the solution to be 1.00 g/mL and the specific heat of the solution to be 4.38 J/g C. a) Calculate the heat of solvation for the KOH mass of solution

heat gained by solution

heat lost by KOH qlost = - qgained qsolvation = -15.4 kJ b) Calculate the molar heat of solvation number of moles of KOH dissolved

molar heat of solvation for KOH

Example: How many grams of propane, C3H8 are needed to combust in order to heat 1150 mL of H2O (4 cups of coffee) from 25.0 C to 98.0 C? The heat of combustion for propane is given as 2043.93 kJ/mol. The formula weight of propane is 44.097 g/mol. Assume d(H2O) = 1.00 g/mL. The key to the problem is recognizing that the heat gained by the water is equal to the heat lost by the combustion of propane. heat gained by water q = m c (Tf Ti) = 1150 g 4.184 J/g C (98.0 C 25.0 C) = 351 kJ heat needed from propane qlost = - qgained qpropane = -351 kJ moles of propane needed found via molar heat of combustion

grams of propane needed

Note: Actually, the amount of fuel needed to heat 4 cups of coffee is considerably higher since most of the heat from combustion heats the surrounding air instead of the coffee.

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HESS LAW
- Enthalpy of reaction can be calculated from other enthalpies of reactions. - Must algebraically manipulate balance equations and reaction enthalpies simultaneously. - The total heat of reaction can be written as a sum of mini-reactions. - Products minus reactants scheme is Hess Law using formation reactions. Example: Find the Hrxn of 2 NO (g) + O2 (g) N2O4 (g), given the Hrxn for the following reactions: N2O4 (g) 2 NO2 (g) 2 NO (g) + O2 (g) 2 NO2 (g) 2 NO (g) + O2 (g) 2 NO2 (g) 2 NO2 (g) N2O4 (g) Hrxn = 57.93 kJ/mol Hrxn = -113.14 kJ/mol Hrxn = -113.14 kJ/mol Hrxn = -57.93 kJ/mol Hrxn = -171.07 kJ/mol 2 NO (g) + O2 (g) + 2 NO2 (g) 2 NO2 (g) + N2O4 (g) 2 NO (g) + O2 (g) N2O4 (g) Enthalpy diagram 2 NO (g) + O2 (g)

-113 kJ/mol -171 kJ/mol 2 NO2 (g)

N2O4 (g)

-58 kJ/mol

Note how reaction is broken up into two steps.

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Example: Find Hrxn of the reaction 2 KCl (s) + H2SO4 (l) 2 HCl (g) + K2SO4 (s), given the following reactions and their enthalpies: HCl (g) + KOH (s) KCl (s) + H2O (l) Hrxn = -203.6 kJ/mol H2SO4 (l) + 2 KOH (s) K2SO4 (s) + 2 H2O (l) Hrxn = -342.4 kJ/mol 2 KCl (s) + 2 H2O (l) 2 HCl (g) + 2 KOH (s) H2SO4 (l) + 2 KOH (s) K2SO4 (s) + 2 H2O (l) Hrxn = +407.2 kJ/mol Hrxn = -342.4 kJ/mol

Adding reactions yields 2 KCl (s) + 2 H2O (l) + H2SO4 (l) + 2 KOH (s) 2 HCl (g) + 2 KOH (s) + K2SO4 (s) + 2 H2O (l) 2 KCl (s) + H2SO4 (l) 2 HCl (g) + K2SO4 (s) Adding enthalpies yields Hrxn = +407.2 kJ/mol Hrxn = -342.4 kJ/mol Hrxn = +64.8 kJ/mol Hrxn = +64.8 kJ/mol

Thus for the reaction 2 KCl (s) + H2SO4 (l) 2 HCl (g) + K2SO4 (s)