FIRST LAW OF THERMODYNAMICS

Zeroth Law
The zeroth law of thermodynamics is a generalized statement about thermal equilibrium between bodies in contact. It is the result of the definition and properties of temperature. A common enunciation of the zeroth law of thermodynamics is: If two thermodynamic systems are in thermal equilibrium with a third, they are also in thermal equilibrium with each other. The law can be expressed in mathematical form as a simple transitive relation between the temperature T of the bodies A, B, and C:

Balance Sheet of Energy Transaction

It is an extension of conservation of energy Let us consider a system, whose energy we want to alter Can be achieved through
Heat operation Work operation both

 Heat Q is supplied to the system, work W is done on the system Energy E of the system will increase Balance sheet will be Q + W = E = Efinal-Einitial Positive signs indicate the gain in the system

Q W = E ( work done by the system) In the differential for the equation will be written as dQ + dW = dE If internal energy is the only energy then dQ + dW = dU First law

Heat change
Assuming a closed system at constant pressure ( internal energy is the only energy) Q+W=U=U2-U1 Since W is mechanical work done under constant pressure QP+P(V1-V2)=U2-U1 QP=(U2+PV2)-(U1+PV1)

 It means that energy change at constant pressure is difference between initial and final values of Ux+PVx the term Ux+PVx is a function represented by H and is called heat content or enthalpy QP=(U2+PV2)-(U1+PV1)=H2-H1=H

 Assuming a closed system at constant volume If volume will not change then work done is zero QV+P(V1-V1)=U2-U1 Qv+P(0)=U2-U1 Qv=U2-U1=U

 Relation between heat change at constant pressure and constant volume H = U + PV H = U +PV If the system is of gases and in normal circumstances the they are ideal PV = nRT or PV = nRT

H = U +PV H = U + nRT

But H is QP and U is QV therefore QP = QV + nRT

The Time-Temperature Graph

We are going to heat a container that has 72.0 grams of ice (no liquid water yet!) in it. To make the illustration simple, please consider that 100% of the heat applied goes into the water. There is no loss of heat into heating the container and no heat is lost to the air. Let us suppose the ice starts at minus 10.0 C and that the pressure is always one atmosphere. We will end the example with steam at 120.0 C.

The Time-Temperature Graph

There are five major steps to discuss in turn before this problem is completely solved. Here they are:
the ice rises in temperature from -10.0 to 0.00 C. the ice melts at 0.00 C. the liquid water then rises in temperature from zero to 100.0 C. the liquid water then boils at 100.0 C. the steam then rises in temperature from 100.0 to 120.0 C

Each one of these steps will have a calculation associated with it. WARNING: many tests questions can be written which use less than the five steps. For example, suppose the water in the problem above started at 10.0 C. Then, only steps 3, 4, and 5 would be required for solution.

The Time-Temperature Graph

graph which is typically used to show this process over time Also, note that numbers 2 and 4 are phases changes: solid to liquid in #2 and liquid to gas in #4

The Time-Temperature Graph

t = the change in temperature from start to finish in degrees Celsius (C) m = mass of substance in grams Cp = the specific heat. Its unit is Joules per gram-degree Celsius (J / g C is one way to write the unit; J g-1 C-1 is another) q = the amount of heat involved, measured in Joules or kilojoules (symbols = J and kJ) mol = moles of substance. Hfus is the symbol for the molar heat of fusion and Hvap is the symbol for the molar heat of vaporization. We will also require the molar mass of the substance. In this example it is water, so the molar mass is 18.0 g/mol.

First Step

The Time-Temperature Graph

Step One: solid ice rises in temperature As we apply heat, the ice will rise in temperature until it arrives at its normal melting point of zero Celsius. Once it arrives at zero, the t equals 10.0 C. Here is an important point: THE ICE HAS NOT MELTED YET. At the end of this step we have SOLID ice at zero degrees. It has not melted yet. That's an important point. Each gram of water requires a constant amount of energy to go up each degree Celsius. This amount of energy is called specific heat and has the symbol Cp.

 72.0 grams of ice (no liquid water yet!) has changed 10.0 C. We need to calculate the energy needed to do this. This summarizes the information needed: t = 10 C The mass = 72.0 g Cp = 2.06 Joules per gram-degree Celsius The calculation needed, using words & symbols is: q = (mass) (t) (Cp)

2nd Step

The Time-Temperature Graph

solid ice melts
Now, we continue to add energy and the ice begins to melt. However, the temperature DOES NOT CHANGE. It remains at zero during the time the ice melts. Each mole of water will require a constant amount of energy to melt. That amount is named the molar heat of fusion and its symbol is Hfus. The molar heat of fusion is the energy required to melt one mole of a substance at its normal melting point. One mole of solid water, one mole of solid benzene, one mole of solid lead. It does not matter. Each substance has its own value. During this time, the energy is being used to overcome water molecules' attraction for each other, destroying the three-dimensional structure of the ice.

The Time-Temperature Graph

The unit for this is kJ/mol. Sometimes you see older references that use kcal/mol. The conversion between calories and Joules is 4.184 J = 1.000 cal. Sometimes you also see this number expressed "per gram" rather than "per mole." For example, water's molar heat of fusion is 6.02 kJ/mol. Expressed per gram, it is 334.16 J/g. Notice how I shifted to Joules instead of kilojoules. This was done to keep the number within the ranges of ones to hundreds. Writing the value using kJ would require I write 0.33416. It is more understandable to write 334.16. Typically, the term "heat of fusion" is used with the "per gram" value.

 72.0 grams of solid water is 0.0 C. It is going to melt AND stay at zero degrees. This is an important point. While the ice melts, its temperature will remain the same. We need to calculate the energy needed to do this. This summarizes the information needed: Hfus = 6.02 kJ/mol The mass = 72.0 g The molar mass of H2O = 18.0 gram/mol The calculation needed, using words & symbols is: q = (moles of water) (Hfus) We can rewrite the moles of water portion and make the equation like this: q = (grams water / molar mass of water) (Hfus)

3rd Step: liquid water rises in temperature

 Once the ice is totally melted, the temperature can now begin to rise again. It continues to go up until it reaches its normal boiling point of 100.0 C. Since the temperature went from zero to 100, the t is 100. Here is an important point: THE LIQUID HAS NOT BOILED YET. At the end of this step we have liquid water at 100 degrees. It has not turned to steam yet. Each gram of water requires a constant amount of energy to go up each degree Celsius. This amount of energy is called specific heat and has the symbol Cp. There will be a different value needed, depending on the substance being in the solid, liquid or gas phase.

 72.0 grams of liquid water is 0.0 C. It is going to warm up to 100.0 C, but at that temperature, the water WILL NOT BOIL. We need to calculate the energy needed to do this. This summarizes the information needed: t = 100.0 C The mass = 72.0 g Cp = 4.184 Joules per gram-degree Celsius The calculation needed, using words & symbols is: q = (mass) (t ) (Cp)

4th Step :liquid water boils

 Now, we continue to add energy and the water begins to boil. However, the temperature DOES NOT CHANGE. It remains at 100 during the time the water boils. Each mole of water will require a constant amount of energy to boil. That amount is named the molar heat of vaporization and its symbol is Hvap. The molar heat of vaporization is the energy required to boil one mole of a substance at its normal boiling point. One mole of liquid water, one mole of liquid benzene, one mole of liquid lead. It does not matter. Each substance has its own value.

 During this time, the energy is being used to overcome water molecules' attraction for each other, allowing them to move from close together (liquid) to quite far apart (the gas state). The unit for this is kJ/mol. Sometimes you see older references that use kcal/mol. The conversion between calories and Joules is 4.184 J = 1.000 cal. Sometimes you also see this number expressed "per gram" rather than "per mole." For example, water's molar heat of vaporization is 40.7 kJ/mol. Expressed per gram, it is 2261 J/g or 2.26 kJ/g. Typically, the term "heat of vaporization" is used with the "per gram" value.

 72.0 grams of liquid water is at 100.0 C. It is going to boil AND stay at 100 degrees. This is an important point. While the water boils, its temperature will remain the same. We need to calculate the energy needed to do this. This summarizes the information needed: Hvap = 40.7 kJ/mol The mass = 72.0 g The molar mass of H2O = 18.0 gram/mol The calculation needed, using words & symbols is: q = (moles of water) (Hvap ) We can rewrite the moles of water portion and make the equation like this: q = (grams water / molar mass of water) (Hvap )

5th Step: steam rises in temperature

 Once the water is completely changed to steam, the temperature can now begin to rise again. It continues to go up until we stop adding energy. In this case, let the temperature rise to 120 C. Since the temperature went from 100 to 120, the t is 20. Each gram of water requires a constant amount of energy to go up each degree Celsius. This amount of energy is called specific heat and has the symbol Cp. There will be a different value needed, depending on the substance being in the solid, liquid or gas phase.

 72.0 grams of steam is 100.0 C. It is going to warm up to 120.0 C. We need to calculate the energy needed to do this. This summarizes the information needed: t = 20 C The mass = 72.0 g Cp = 2.02 Joules per gram-degree Celsius The calculation needed, using words & symbols is: q = (mass) (t ) (Cp)

72.0 grams of ice has changed from -10.0 C to 120.0 C. The energy calculation for this change required five steps
1. 1483.2 J t = 10 (solid) 2. 24.08 kJ melting 3. 30124.8 J t = 100 (liquid) 4. 162.8 kJ boiling 5. 2908.8 J t = 20 (gas)

Total will be vector sum of all five steps

Home Work
Heat Capacity