Energetics II (Topic 13) Flashcards
What is lattice enthalpy of formation (Delta_latticeH)
Enthalpy change when 1 mole of a solid ionic compound is formed from it’s gasesous ions under standard conditions.
Ca^2+(g) + 2Cl^-(g) -> CaCl_2
Ions in the gaseous state forming a solid ionic compound
What is Enthalpy change of atomisation (symbol)
The enthalpy change when 1 mole of gaseous atoms is made from an element in its standard state. This is ALWAYS an endothermic process. You need energy in to do this
1/2 F_2 (g) –> F (g)
Turning a standard version of an element into a single gas atom
What is 1st electron affinity (symbol)
Enthalpy change when 1 mole of gaseous 1- ions are made from 1 mole of gaseous atoms
O(g) –> O^- (g)
Adding an electron to something that is neutrally charged, adding the first electron
What is 2nd electron affinity (symbol)
Enthalpy change when 1 mole of gaseous 2- ions are made from 1 mole of gaseous 1- ions
O^-(g) –> O^2-(g)
Adding a second electron, adding an electron to something that is already negatively charged
What is ionic bonding
Ionic bonding is formed from oppositely charged ions, there is an electrostatic attraction between the two ions. This electrostatic attraction is what formed the ionic bond
What factors influence the strength of the ionic bond
The size of the charge on the ion.
The size of the ion/ionic radii
How does size of the charge of the ion influence the strength of the ionic bond
The bigger the charge on an ion, the stronger the electrostatic attraction between ions. An ionic bond between a 2+ and a 2- ion is stronger than a bond between a 1+ and 1- ion.
K+ and Cl- has an mp of 770 C, Ca^2+ and O^2- has a melting point of 2572 C
What effect does a stronger ionic bond have on melting point and boiling point
The stronger the ionic bond, the more energy is required to overcome electrostatic forces of attraction, so they have higher melting and boiling points.
What do you need to break ionic bonds apart
Quite a lot of heat energy
How does the size of the ion/ionic radius influence the strength of the ionic bond
The smaller the ion/ionic radius, the stronger the electrostatic attraction between ions.
Na+ and Cl - has an mp of 801 C, K+ and Cl- (K is bigger ion than Na) has a mp of 770 C.
WHY does size of ion/ionic radius affect the strength of an ionic bond
Smaller ions can pack together more closely because of their size, so the + and - charges are much closer together. So more energy is required to overcome these stronger forces. So mp and bp increase as a result
What is charge density
Higher charge in a smaller ion means the ion has a high charge density. A high charge is concentrated in a small area.
What effect does higher charge density have on the strength of an ionic bond
Generally, the smaller the ion, and the higher the charge, the stronger the electrostatic attraction and therefore the higher the mp. Higher charge density means stronger ionic bond.
What does exothermic mean
It gives out heat energy, meaning the system loses heat energy/enthalpy
What does endothermic mean
It takes in energy, meaning the system gains heat energy, so you need energy in to make the process happen.
What is enthalpy of formation (symbol)
Enthalpy from the formation of 1 mole of a solid ionic compound from elements in their standard states. This is an exothermic process
What is enthalpy change of first ionisation
Energy required to remove the first outermost electron from 1 mole of gaseous atoms. Enthalpy change when 1 mole of gaseous atoms is turned into 1 mole of gaseous 1+ ions and 1 electron.
What is the Born-Haber cycle used for and why
To calculate lattice enthalpies because you can’t calculate this value through experiments
How do you start a Born-Haber cycle
You always start by drawing the bottom line with your solid compound which you want to form through lattice formation on top of the bottom line. Remember, always include state symbols.
______LiCl(s)_____
What do you do after the drawing bottom line and writing the solid you want to form of a Born-Haber cycle
You write the first route to your product, which is through standard enthalpy change of formation above the product.
These are the two elements required to make LiCl(s) in their standard states.
__Li(s) + 1/2 Cl_2 (g)___
_v_______________________________LiCl(s)____
How is the Born-Haber cycle organized
The higher up the step, the more energy the step has. This is why we put Li(s) + 1/2 Cl_2 (g) just above LiCl(s), because that step has more energy.
What does the direction of the arrows in the Born-Haber cycle mean
The direction the arrow is pointing signals the energy change. For example in the step below, the arrow going from standard enthalpy of formation to the product is pointing down. This means that the process is exothermic, so it gives out heat energy.
__Li(s) + 1/2 Cl_2 (g)___
_v_______________________________LiCl(s)____
If the arrow was pointing up, that means the process would be endothermic, so it takes in heat energy. Each type of enthalpy change has the quality of either being exothermic or endothermic.
How do you know whether an enthalpy change process is exothermic or endothermic
Forming bonds is exothermic, breaking bonds is endothermic. Each type of enthalpy change process has its own exothermic vs endothermic process, But memorize the quality for each process.
When drawing arrows in a Born-Haber cycle, what should you make sure to do
Make sure that the tip and the tail of the arrow touches the level lines. Otherwise you may lose marks
When drawing arrows in a Born-Haber cycle, what should you make sure to do
Make sure that the tip and the tail of the arrow touches the level lines. Otherwise you may lose marks
How does the Born-Cycle work in analogy form?
Born-Haber is a cycle of different events. If you wanted to form LiCl(s), you just go down ROUTE 2 through standard enthalpy of formation, or you could go up and around ROUTE 2 and form it through standard LATTICE enthalpy of formation. In the same way, you can get to school by going from the springs/spinneys route, or you could go around the Springs Souk route. You end up at the same location, but one route may be longer than the other.
What is the goal when drawing a Born-Haber cycle?
You start with your solid compound at the bottom, and draw route 1 above it, standard enthalpy of formation of that compound. Then, you must go from that step to the phase where you have a positive gaseous ion and a negative gaseous ion to allow for LATTICE enthalpy of formation. This is the end goal step of a Born-Haber cycle. Each step brings you closer to this finish line.
After drawing the bottom line and route 1 of the Born-Haber cycle, what must you do next
After that, you have to work towards getting your elements from their standard states, to their gaseous ion forms. In this example, we must do the first enthalpy of atomisation of chlorine in order to get it from 1/2 Cl_2(g) to just Cl (g). All atomisation reactions are endothermic. You need heat to convert, so we need energy in. This is why the arrow is pointing up. We are going from a diatomic molecule to a single atom because we only need 1 chlorine for LiCl(s)
_A___Li(s) + Cl (g)_______
__Li(s) + 1/2 Cl_2 (g)___
_v_______________________________LiCl(s)____
After converting one of your elements from it’s diatomic form to a single atom through enthalpy change of atomisation, what is your next step in your Born-Haber cycle
The goal is to convert all elements from their standard states into their charged gaseous forms. In our example, we already have Cl(g) in its single atom gaseous form, so we must now convert Li(s) into its gaseous form.
This is also enthalpy change of atomisation (endothermic) since we are turning lithium solid, into lithium gas
_A___Li(g) + Cl (g)______
_A___Li(s) + Cl (g)______
__Li(s) + 1/2 Cl_2 (g)___
_v_______________________________LiCl(s)____
What determines the order of the steps in a Born-Haber cycle when it is in the same section i.e in converting the elements from their standard states to their gaseous forms
The order of these steps is determined by their energy levels, so which ever one has the lowest energy increase will be put first. If turning 1/2 Cl_2 (g) to Cl (g) is a lower energy increase than turning Li(s) to Li(g), then the Cl(g) step will go below, and the Li(g) step will go above
What are the sections of steps in a Born-Haber cycle
- Desired Compound on bottom line
- Standard Enthalpy of formation Showing route 1
- Going from standard enthalpy of formation to elements in their gaseous forms through standard enthalpy of atomisation
- Providing a charge to atoms in their gaseous forms through 1st ionisation energy THEN 1st electron affinity.
- Turning charged gaseous ions into the lattice through standard enthalpy of LATTICE formation
After both elements are in their gaseous form, what is the next step in the Born Haber cycle
You have to provide charge for the elements to turn them into ions. They must be gaseous ions in order for standard LATTICE formation enthalpy to work. We remove an electron from lithium through enthalpy change of 1st ionisation, giving it a positive charge, resulting in a free electron. Ionisation is always endothermic. This free electron is used in the next step.
_A_____________________________Li+ (g) + Cl(g) + e-
_A___Li(g) + Cl (g)______
_A___Li(s) + Cl (g)______
__Li(s) + 1/2 Cl_2 (g)___
_v_______________________________LiCl(s)____
After one of your elements has been ionised with a positive charge, what is the next step in the Born Haber cycle
Now, the free electron that was ionised from the element which has gained a positive charge. This free electron is given to the other element to form a negative ion. This is done through enthalpy change of 1st electron affinity. This is an EXOTHERMIC PROCESS, SINCE WE ARE FORMING BONDS. Breaking bonds is endothermic. But the electron is joining the second element to make a negative ion, which means it is forming a bond. Since the previous step was the highest energy step, that is the top level. This electron affinity step is going back down in energy as it is exothermic.
Cl(g) gains an electron, turning it into a Cl- (g) ion.
_A_____________________________Li+ (g) + Cl(g) + e-______________________
A___Li(g) + Cl (g)______ __Li+ (g) + Cl- (g)_____v
_A___Li(s) + Cl (g)______
__Li(s) + 1/2 Cl_2 (g)___
_v_______________________________LiCl(s)____
When is something considered 1st electron affinity or 1st ionisation energy
1st electron affinity is when you are adding an electron to a neutral atom, as it is the first electron added before becoming negative. 1st ionisation energy when you are removing an electron from a neutral atom, as this is the first electron removed before becoming positive.
What is the FINAL step of the Born-Haber cycle
Going from gaseous ions to forming your solid compound with standard enthalpy of LATTICE FORMATION. This is the finish line we were aiming towards. This is EXOTHERMIC, because we are FORMING BONDS, even if they are ionic bonds, we are still forming bonds. This step actually takes us all the way to the bottom line, as we have just formed our desired solid compound.
_A_____________________________Li+ (g) + Cl(g) + e-______________________
A___Li(g) + Cl (g)______ __Li+ (g) + Cl- (g)_____v
_A___Li(s) + Cl (g)______
__Li(s) + 1/2 Cl_2 (g)___
v_______________________________LiCl(s)______________________________v
What is the difference between standard enthalpy change of formation and standard enthalpy change of LATTICE FORMATION
In standard enthalpy change of formation, two species combine covalently from their standard states. In standard enthalpy change of LATTICE FORMATION, two gaseous IONS combine electrostatically.
What is the difference in enthalpy between route 1 and route 2 of a Born-Haber cycle
There is no difference in total enthalpy. It works like the Hess’s cycle. As long as reactants and products are the same, the total enthalpy change is the same regardless of the route.
How do you calculate the value of Lattice enthalpy of formation from a Born-Haber cycle with given values
Put all the values next to each step, if you are going along the arrow, keep the sign of the value given the same. If you are going against the direction of the arrow, then flip the sign.
How do you make sure the given values match up to the processes in your Born-Haber cycle. For example, you are given enthalpy of atomisation of Cl_2 (g)= 242, but on your cycle, the step needs the atomisation of 1/2 Cl_2 (g)
Simply alter the value given to the desired result which is needed for the step. DO NOT FORGET TO DO THIS. From the example, you simply do 242/2 = 121, which is the value you use. Remember to check if you are going against or along the arrow’s direction to see which sign to put.
What is the analogy to help you solve Born-Haber cycle problems
Imagine your 2 routes as Sheikh Zayed and Al Khail Road. Sheikh zayed is faster and more direct, but today Sheikh Zayed is blocked off because of the 10km run for the 30x30 challenge. So you have to take Al Khail road to get to your destination. If you are asked to solve the energy for one step, you have to go all the way around and use algebra to find the value which is asked for.
How do you test if you got the right answer when solving Born-Haber cycle problems
Think about which step they are asking for and whether it is exothermic or endothermic. For example, they ask for standard enthalpy of LATTICE formation, which you know is exothermic. If your answer is on the right lines, you should get a negative value for your answer.
Once you have worked out the final value on a Born-Haber cycle problem, how do you test it a final time to see if it is correct.
Follow the Born-Haber cycle from one side to the other, you can choose ANY step as your starting point, using the arrow rules. If the answer to your calculation = 0, then the value you worked out is correct!
What is the difference between a regular Born-Haber cycle and a Born-Haber cycle that is between ions of 2+ and 2- charge.
In a 2+ and 2- charge Born Haber cycle, there are some extra steps. The first difference is that there are 2 ionisation steps for the ion which will become positive. So Mg (g) going to Mg+ (g) is step 1, and Mg+ (g) going to Mg 2+ (g) is step 2. Both are endothermic so they go up as normal. The second difference is that when the second element becomes negatively charged, the first electron affinity is going down, exothermic as normal, but the second electron affinity goes back up, it is endothermic. Then the final step of enthalpy change of LATTICE FORMATION is exothermic, arrow goes down as normal.
_A____________________________Mg^2+ (g) + 2O (g) + 2e-________________________________________
A___Mg+ (g) + 2O(g) + e- __________A____Mg 2+ (g) + O^2- (g)____
_A___Mg(s) + 2O (g) __ _V_______Mg 2+ (g) + O- (g) + e-________
______Mg(s) + O_2 (g)__
_v_________________________________________MgO(s)___________________________________v______
Which order do you do enthalpy of ionisation and enthalpy of electron affinity in a Born-Haber cycle between ions of 2+ and 2- charge.
First, ionise the element that is going to become a 2+ charge fully. So do a step with 1st ionisation energy enthalpy, then a step with 2nd ionisation energy enthalpy. Get your electrons both free first, giving you 2e-. After THAT, you do the electron affinity for the second element which is going to become a 2- charge. Remember, going from O^1- to O^2- is ENDOTHERMIC, arrow goes up.
In a Born-Haber cycle between 2+ and 2- charge ions, why is 2nd electron affinity endothermic
Because energy is needed to add an electron to a negative ion. Repulsive forces try to prevent you doing this between 2 negative species, so you have to add energy in to force the electron to bond, meaning the step is endothermic.
Why can theoretical and experimental values of lattice enthalpies be different
This depends on how purely ionic the compound is. The more ionic the bonding, the closer the experimental value will be to the theoretical. There are instances of ionic bonding which are impure, which have some other bonding type, like covalent, mixed in.
What is the perfectly ionic model that we assume when calculating theoretical lattice enthalpies
- Ions that are perfectly spherical
- The charge is evenly distributed in this sphere (point charge)
What does it mean when you carry out an experiment and the theoretical lattice enthalpy is different than the value you calculated through experimental methods
The compound being experimented on DOESN’T follow the perfectly ionic model and has some covalent characteristics. Non-purely ionic compounds are more common than purely ionic ones.
What happens in an impurely ionic compound to make it impure
Most of the time, the positive ion distorts the charge distribution in the negative ion. We say the positive polarises the negative ion.
(INSERT PICTURE from 28:03 Allery Energetics II Revision)
What is the relation between more polarisation of an ionic compound and how purely ionic it is
The more polarisation we get, the more covalent character there will be, and therefore it will be less purely ionic
What can lattice enthalpy values tell us about the bonding of an ionic compound and how
How purely ionic a compound is. The closer the experimental lattice enthalpy value is to the theoretical, the more purely ionic a compound is.