General Chemistry-Thermochemistry Flashcards
What is the 1st law of thermodynamics?
Energy is never created nor destroyed but simply changed from one form to another
What is considered the system?
The matter that is being observed- the total amount of reactants and products in a chemical reaction.
Is the boundary between system and surrounding environment permanetly fixed?
No, it can be moved
What are the three characterizations of a thermodynamic system?
Isolated
Closed
Open
What is an isolated thermodynamic system? Example?
The system cannot exchange energy (heat and work) or matter with the surroundings; for example, an insulated bomb calorimeter.
What is a closed thermodynamic system? Example?
The system can exchange energy (heat and Work) but not matter with the surroundings, for example a steam radiator
What is an open thermodynamic system? Example?
The system can exchange both energy (heat and work) and matter with the surroundings, for example a pot of boiling water.
What is the definition of a process?
When a system experiences a change in one or more of its properties (such as concentrations of reactants or products, temperature, or pressure).
Association with a change of the state of a system
How are some processes unique?
Some processes are uniquely identified by some property that is constant throughout the process. Many of these processes create special conditions that allow the first law of thermodynamics to be simplified.
What is the simplified equation for the 1st law of thermodynamics?
/\U= Q - W
What do the letters represent in the simplified equation for the 1st law of thermodynamics?
/\U: The change in internal energy of the system
Q: is the heat added to the system
W: is the work done by the system
When do isothermal processes occur?
When the system’s temperature is constant
What does constant temperature imply in a isothermal process?
The total internal energy of the system (U) is constant throughout the process
Why is the total internal energy of an isothermal system constant throughout the process?
Temperature and internal energy are directly proportional. When U is constant, /\U=0, and the first law simplifies to Q=W (the heat added the the system equals the work done by the system).
How does an isothermal process graph appear?
As a hyperbolic curve
What are the axes used to look at an isothermal process graph?
Pressure and volume (P-V Graph)
How is work represented on an isothermal process graph?
Work is the area under a curve
When does an adiabatic process occur?
When no heat is exchanged between the system and the environment; thus the thermal energy of the system is constant throughout the process.
When Q=0, how does the 1st law of thermodynamics simplify?
/\U = -W (the change in internal energy of the system is equal to the work done on the system [the opposite of work done by the system]).
How does adiabatic process appear on a P-V graph?
Hyperbolic
When do Isobaric process occur?
When the pressure of the system is constant
Which processes are common? Why
Isothermal and isobaric processes are common because it is usually easy to control temperature and pressure.
How do isobaric processes appear on a P-V graph?
Isobaric processes do not alter the 1st law of thermodynamics, but appear as a flat line.
What are isovolumetric processes?
Processes that experience no change in volume
What is another name for isovolumetric processes?
Isochoric
Why is no work performed in an isovolumetric process?
Because the gas neither expands nor compresses, no work is performed
How does the 1st law of thermodynamics simplify in an isovolumetric process?
/\U =Q (The change in Internal energy is equal to the heat added to the system.)
How does an isovoumetric process appear on a P-V graph?
Vertical Line. The area under the graph which represents work done is zero
How can processe by further classified?
Spontaneous or nonspontaneous
What is a spontaneous process?
One that can occur by itself without having to be driven by energy from an outside source
How do you determine if a process will be spontaneous or nonspontaneous?
Calculating the change in the Gibbs free energy (/\G) for a process, such as a chemical reaction.
What are temperature dependent processes?
The process will be temperature dependent, that is spontaneous at some temperatures and nonspontaneous at others.
What is a common method for supplying energy for nonspontaneous reactions?
Coupling nonspontaneous reactions to spontaneous ones.
What are macroscopic properties?
Properties that describe the system in an equilibrium state.
What is another name for macroscopic properties?
State functions
What can macroscopic properties not describe?
The process of the system; that is, how the system got to its current equilibrium.
Macroscopic properties can compare what?
One equilibrium state to another
What are process functions?
The pathway taken from one equilibrium state to another
What are the most important process functions?
Work (W)
Heat (Q)
State function include what?
Pressure (P) Density (p) Temperature (T) Volume (V) Enthalpy (H) Internal energy (U) Gibbs Free Energy (G) Entropy (S)
When do state functions change?
When the state of a system changes from one equilibrium to another
Are state function independent of one another?
Not necessarilly, For example Gibbs free energy is related to enthalpy, temperature, and entropy
What are the standard conditions of systems with various temperatures, pressures, and equilibrium states?
25 degrees C. (298 K)
1 atm Pressure
1 M concentration
Is standard conditions the same as standard temperature and pressure?
No.
What is standard temperature and pressure (STP)?
The temperature is 0 Degrees C (273 K)
1 atm Pressure
When are standard conditions used and when are STP conditions used?
Standard conditions are used for kinetics, equilibrium, and thermodynamics
STP are used for ideal gas calculations
What is standard state of a substance?
Under standard conditions, it is the most stable form a substance.
What is the standard state of important elements at standard conditions?
H2 (g) H2O (l) NaCl (s) O2 (g) C (s, graphite)
When is it important to know the standard state of an element?
For thermochemical calculations, such as heats of reactions and heats of formation.
What are the names of the changes in enthalpy, entropy, and free energy that occur when a reaction take place under standard conditions? Symbols?
The Standard enthalpy (/\H degree) Standard Entropy (/\S degree) Standard Free energy changes (/\G degree)
What does the degree sign represent in the symbols of standard enthalpy, entropy and free energy changes?
Zero, as the standard state is used as the “zero point” for all thermodyamic calculations.
What are phase diagrams?
Graphs that show the standard and nonstandard states of matter for a given substance in an isolated system, as determined by temperature and pressure.
What are phase changes?
(Solid Liquid Gas)
What is important to know about phase changes?
They are reversible and an equilibrium of phases will eventually be reached at any given combination of temperature and pressure
What happens to H2O at 0 Degrees C and 1 atm?
Ice and water exist in equilibrium
How much water vapor is present when H2O reaches equilibrium in liquid and gas state?
3% water vapor by mass
Phase equilibrium is analogous to what?
The dynamic equilibria of reversible chemical reaction: the concentrations of reactants and products are constant because the rate of the forward and reverse reactions are equal.
Temerpature of a substance in any phase is related to what?
The average kinetic energy of the molecules that make up a substance
What is evaporation?
Some of the molecules near the surface of the liquid may have enough kinetic energy to leave the liquid phase and escape into the gaseous phase.
What is another name for evaporation?
Vaporization
What happens each time the liquid loses a high-energy particle?
The temperature of the remaining liquid decreases.
Evaporation is what type of process?
Endothermic process for which the heat source is the liquid water.
What is boiling?
A specific type of vaporization that occurs only under certain conditions.
Boiling is the rapid bubbling of the entire liquid with rapid release of the liquid as gas particles.
What is the difference between normal evaporation and boiling?
Evaporation can happen in all liquids at all temperatures,
Boiling can only occur above the boiling point of a liquid and involves vaporization through the entire volume of the liquid.
What is condensation?
In a covered or closed container, the escaping molecules are trapped above the solution. These molecules exert a countering pressure, which forces some of the gas back into the liquid phase.
When is condensation facilitated?
By lower temperature or higher pressure
What is vapor pressure?
The pressure the gas exerts over the liquid at equilibrium
When does vapor pressure increase? Why?
As temperature increase because more moleucles have sufficient kinetic energy to escape into the gas phase.
What is boilig point?
The temperature at which the vapor pressure of the liquid equals the ambient (also known as external, applied, or incident) pressure.
Will solids have molecule movement?
Each atom or molecule can undergo motions about some equilibrium position
When do the vibrational motions of molecules in a solid state increase?
When heat is applied
What happens to molecules when temperature is increased?
The molecules have greater freedom of movement and energy disperses
What is the transition from the solid state to the liquid state called?
Fusion or Melting
What is the transition from the liquid state to the solid state called?
Solidification, Crystallization or Freezing
What is the temperature of a solid liquid change or a liquid solid change called?
Melting point or freezing point
What has distinct melting points and what has ranges of melting points?
Pure crystalline solids have distinct, very precise melting points, amorphous solids such as glass, plastic, chocolate and candle wax tend to melt or solidify over a larger range of temperatures, due to their less-ordered molecular structure