Introduction to spectroscopy, Energy and Bonding Spring Semester Flashcards
How do thermodynamics determine chemical reactivity?
Thermodynamics refers to the transfer of heat and work, meaning thermodynamic factors control whether a reaction will take place or not. Work is done as a result go of motion against an opposing force (molecules vibrating).
How do kinetics determine chemical reactivity?
Kinetic factors determines the rates of a reaction, a reaction may take place but on an unreasonable timescale.
What is the systems and surroundings in a thermodynamic problem?
System > the part of the Universe we want to study
Surroundings > the part of the universe outside of the system
A change in energy can determined by measuring energy transfer to and from the surroundings.
What is the equipartition Theory?
This states that energy is shred equally amongst all energetically accessible degrees of freedoms of a system. This means each degree of freedom contains energy 1/2kT or 1/2RT per mole.
How to calculate the number of degree of freedom?
linear molecules = 3N-5
Non-linear molecules = 3N-6
What is the definition of internal energy?
The sum of all the kinetic energy contributions and potential energy contributions (U). it cannot be measured by ΔU and be thought about the capacity to do work.
U = total kinetic energy + total potential energy
What is the molecular origin of internal energy?
- Molecules contain potential energy, because of their position relative to one another
- Molecules are neutral, and extent attractive and repulsion forces on one another
How do you calculate the average kinetic contribution to the molecular internal energy?
- With a linear molecule is can rotate about two axis so rotational contribution is 2x(1/2)RT
- A nonlinear molecule can rotate about three axis so has a rotational contribution is 3x(1/2)RT
- A gas has a translation contributions of 3x(1/2)RT
it is then calculated add of the kinetic contribution together
e.g. for a non linear molecule
(3x1/2kT) + (3x1/2kT) = 3kT
then multiplying by k or R and T
T in kelvin = stated in question
Then R (idea gas constant) used to calculate energy per mole and K (Boltzmann constant) used to calculate energy per molecule.
What causes changes to internal energy?
Internal energy changes by transferring energy to or from the system as heat
- If work is done BY a system then its internal energy decreases
- If work is done ON a system then internal energy increases and it capacity to do work increases
What is the first law of thermodynamics?
In a isolated system, the change in internal energy is the sum of the energy change due to transfer of heat (q) and work (w) both in joules. energy cannot be created or destroyed, only transferred.
ΔU = q + w
w is positive if work is done ON the system and negative if work in door BY the system
q is positive is heat is supplied to the system and negative if heat if released form the system
What are two types of work a system can do?
- expansion (change in volume of the system by a reaction with gaseous products)
- non-expansion (work that does not involve a change in volume)
How do you calculate the work done in reversible expansions?
Reversible expansion
w = nRTln(Vf/Vi)
w = work doen (joules)
n = moles
R = ideal gas
T = Temp (k)
Vf = final volume (dm^3)
Vi = initial volume (dm^3)
How do you calculate the work done in irreversible expansions?
Irreversible expansion
w = -PexΔV
Pex = pressure (Pa)
Δv = change in volume (m^3)
What are the properties of state functions in calculations?
internal energy is a state function, the means that the value depends only on the initial and final sates of the system but not on the route taken (volume, temp and pressure are also state functions)
How do you use the properties of state functions in calculations?
The change in the state of the system is independent of how the change was brought about.
How can internal energy changes be measure with a calorimetry?
Calorimeters are used to measure the internal energy change of a reaction initiated inside a constant volume. Any rise and fall in the temperature os the water bath can be equated to heat released by the reaction. It happens without transferring heat or mass between the system and surroundings.
As the reaction occurs at a constant volume the flow of heat corresponds to the change in internal energy and be calculated as
ΔU = -CcalΔT
Ccal = experimental constant (heat capacity/calorimeter constant)
T = temperature (k)
per mole is workout by dividing by the number of moles of the substance
What is the definition of enthalpy?
Enthalpy (H) is the heat transferred by a chemical reaction at a constant pressure (in an open system atmospheric pressure does not change), its a state function.
H = U +pV
p = pressure
V = volume
U = work (j)
As it take place a constant pressure more frequently written as
ΔH = q
if the enthalpy is negative the reaction is exothermic and if its positive endothermic.
ΔH = H(products) - H(reactants)
What is the definition of heat capacity?
Heat Capacity (C) is a measure of how much heat must be supplied to raise the temperature by a given amount. Specific heat capacity normalise to mass
Cs - q/ mΔT
Moor heat capacity is normalised to moles
Cm = q/nΔT
What is the definition of standard enthalpy changes?
The enthalpy change which occurs when one mole of a compound is formed from its elements under standard conditions, and with everything in its standard state.
How do you estimate enthalpy changes from internal energy changes?
For reactions involving solids the volume of product and recant is very similar change is volume is equal to 0 and enthalpy change equivalent to change in internal energy.
ΔrH = ΔrU
For gases volume differs dramatically so assuming ideal behaviour
ΔrH = ΔrU + ΔngasRT
Δn = n of products - n of reactants
R = ideal gas
T = temp (K)
How do you calculate standard reaction enthalpies form Hess’ law?
The overall enthalpy changer is the sum of the enthalpy changes of the steps into which the reaction can be divided.
Creating a hess diagram of formations
ΔH = ΔH reactants to elements + ΔH elements to products
How do you estimate reaction enthalpies using average bond enthalpies?
Bond enthalpies is a measure of the bond strength, its the standard enthalpy change for the dissociation of a molecule in the gas phase into atoms in the gas phase. it can be used as an alternative to calculate reaction enthalpy.
XY (g) –> X(g) + Y(g)
How do you use Kirchhoff’s law to calculate standard reaction enthalpies at another temperature?
The enthalpy of reactant and products increases with temperature. The rate of increase in enthalpy with temperature is the heat capacity at constant pressure as can be written as
ΔCp = total nCp (products) - total nCp (reactants)
What is the second law of thermodynamics?
The entropy of an isolated system increases during any spontaneous process, increasing total entropy of the universe. Entropy is change is grater than 0.