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Relatino betwene work and energy
w = E_kf-E_ki
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Kinetic Energy
Energy posessed by a body by virtue of being in mostion
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Potential ENergy
Energy posessed by a body by virtue of position
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System
A specific segmentof hte world with deffinite boundaries on which we focus our attention
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Surroundings
The part of the world immediately surrounding a system
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Universe
System and its surroundings
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Open system
Can transfer heat and material
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Closed system
Can only transfer heat
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Isolated system
Can transfer neither heat nor matter
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Intensive property
Not a function of quantity
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Extensive propety
Directly a function of quantity
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Equation of state
An equation that describes the condition of a system as a function of intensive properties
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Equilibrium
The systems variables of state are not changing with respect to time
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Heat
The kinetic energy of molecualr motion
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Zeroeth law of thermodynamics
- If A and B are in thermal equilibrium
- And B and C are in thermal Equilibrium
- Then A and C are in thermal Equilibrium
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Boyles Law
Applies under Isothermic Conditrions. If temperature and nubmer of mols are held constant then PV=Constant
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Isotherm
Temperature is held constant
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Isobaric
Pressure is held constant
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Gay-Lussacks Law
If Pressure and mols are fixed then V/T =Constant
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3 Assumptions of ideal gas law
- 1) gas is assumed to be composed of individual particles whose actual dimensions are small in comparison to the distance between them.
- 2) These particles are in constant motion and therefore have kinetic energy.
- 3) Neither attractive nor repulsive forces exist between the particles.
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N
Number of molecules present
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Pressure in terms of mean square speed
P=
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Average Kinetic Energy of a molecule in a system
e=.
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Partial Pressure
Pressure exerted by a single component of a gas mixture. Defined by molar fraction* pressure total
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Grahms law of Effucsion
R
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Collision frequency
- How many collisions pe second does a molecule experieince
- units : 1/s
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Collision Density
- How many colisions per unit of second per volume occur?
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Mean free path
- How far a molecule travels before a collision
- distnace
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ump
Most probable velocity. Peak of maxwell curve
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z
- Compression factor
- =
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z>1
Repulsive forces dominate (b term from nonideal gas)
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Z<1
Attractive forces dominate (a term)
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Van Der Waals equation
Uses a to account for attraction and b to account for repulsion
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Adiabatic
No change in Heat (Q)
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Terms in the maxwell constant of dN/Ndu
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Boltzman distribution
- )
- Maps likely distribution of particle velocities
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Incremental volume
- 4\
- Accoutns for incremental volume in maxwell distribution sphere
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Maxwell normalization factor
- NOrmalizes maxwell distribution by total molecules likely to be present
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- Average speed of a molecule in system given by maxwell normalization factor. Actually less common than
- Formula:
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Least common of the important speeds in maxwell distribution, this is the root mean square speed.
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Average kinetic energy per molecule formula and function of
- e==.5mu2This is a function primarilly of temperature.
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When u is not velocity, what is it? (fucking headache)
- Internal energy: the internal energy of a molecule is the sum of its heat and work
- u=q+w
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First law of thermodynamics
Energy can neither be created nor destroyed. Only moved.
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What are the Five macroscopic properties
Pressure, Temperature, Volume, Mass, Enegy
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What are state functions?
The macroscopic properties that define a substance
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What happens if we fix 3 of the state functions
The other two are then known
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What is path dependence?
A path dependent function is dependent on how one reaches a point. Using a mountain analogy: Height to reach a point is always constant, distance is a function of the route you take to reach tehat point.
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Are state functions path dependent?
No. They are not. It is part of what makes them state functions.
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Equilibrium states
Points at which without an external operator acting, a system will hold in a steady state over time.
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3 Criteria for equilibrium state
The mechanical properties, chemical properties and temperature throughout a system must be uniform for something to be in an equilibrium state
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Reversible vs Irreversible processes
If a system is changed slowly enough to maintain an equilibrium state, it is considered a reversible process.
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Sign convention for heat (q)
If a system absorbs heat, q is positive. If a system loses heat, q is negative
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Sign convention for work on a system (w)
- If work is done on a system (work flows in), then w is positive
- If work is done by a system (work flows out), then w is negative.
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q
- Heat of system. function ot work and internal energy
- q=
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What can we know about internal energy of a system over an operation
Its change. We do not know how much internal energy a system posesses, only how much it changes over time
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What type of properties are heat and work
Path properties. They are dependent entirely on path and not functions of state. they are inexact integrals.
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Nature of intenral energy (u): What are the 3 things that contribute
- 1) kinetic energy of motion of hte individual molecules
- 2) Potential eneryg that arise form interactions between molecules
- 3) Kinetic and potential energy of nuclei and elctorns with inthe individual molecules.
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What are the four types of work
- Chemical: energy of breaking chemical bonds
- Elctrical: Work performed by current
- Mechanical : Gross work of physical motion of masses
- Osmotic: Transportation and concentration of chemicals
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What is work defined as?
A force over distance. IE ENERGY
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How do we define reversible work in thermodynamics? (Form and two notes)
w rev=-\
- Note that if P is not constant, we must deffine it as a function of volume before doing this calculation.
- Note that dv implies an infintessimal volume change.
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Is more work done through reversible or irreversible processes? What do graphs look like?
- If a process is reversible, it requires more work to do because pressure is assumed constant constant and graph of change is curved.
- If a process is irreversible, then less work is required as both pressure and volume are assuemd to change. Graph is straight drop of pressure and the straight change of volume.
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Which type of process(Reversible or irreversible ) generates more heat? Why?
- We assume inc U to be constant.
- With this as a given and the realization that
- there will be more heat generated by irreversible work because there is less actual work done.
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What is formula and assumption of irreversible work?
- Irreversible work is assumed to happen suddenly. Too suddenly to be considered incremental. As such, we use the final pressure to calcualte
- wirr=-P2(Vfinal-Vinitial)
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When is work maximized?
When a process is reversible.
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What happens to internal energy for an isochoric process?
It is only a function of change of heat as volume is 'fixed'
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Isochoric
Constant volume
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What is Enthalpy (H)?
- Enthalpy is a state function equal to :
- H= U + PV = internal energy + PRessure * Volume
- This deffinition is only valid if all work is PV work.
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What is the change in heat (q)for a constant pressure system?
inc
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Endothermic process definition
- One in which q and w are positive.
- This implies that heat and work flow into system.
- This also implies that the surroundings will lose heat and feel colder.
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Exothermic Process
One in which q and w are negative.This implies that heat and work flow out of the system. This also implies that the surroundings will gain heat and feel hotter in temperature.
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What are the two forms of heat capacity and why do we have them?
- Isochoric: Constant Volume
- Isobaric: Constant Pressure
Heat capacity is not a state function. It fluctuates fased on sate functions and as suc hwe need to account for environmental conditions.
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What should we know about Cv and what is its formula?
- This is isochoric heat capacity. It implies that there is a constant volume in system. In general, it is less like lab work/real systems.
- Due to the lack of change in volume, we asusme this to be purely a function of intenral energy
- Its formula is: Cv=
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What should we know about CP and what is its formula?
- This is Isobaric heat capacity. While pressure is constant, volume may vary and we thus may need to account for work. As such it is a function of Enthalpy (H) and is far more common in the lab.
- Cp = \gr
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What is heat capacity?
How much heat energy (Joules) a kilogram of a substance must absorb to increase by 1 K in temperature.
It varies with temperature and type of system.
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How are Isochoric and Isobaric heat capacity related?
Cpm =Cvm +R
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When can you use either form of heat capacity to find change in heat?
When working with an ideal gas, either form of heat capacity is equally valid.
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What is formula for change in enthalphy?
i
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What is formula for change in internal energy?
in
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