Physical chemistry Flashcards
3.1.1
What are the fundamental particles? relative charges? relative masses?
Proton:
- relative charge = +1
- relative mass = 1
neutron:
- relative charge = 0
- relative mass = 1
Electron:
- relative charge = -1
- relative mass = 0.0005 (negligible - very small)
3.1.1
define: Atomic number, Mass number, Isotopes, Relative Atomic mass, Relative isotopic mass
Atomic number:
The number of protons in the nucleus of an atom. Denoted by Z
Mass number:
The number of protons + neutrons in the nucleus Denoted by A
Isotopes:
atom with a different no. of neutrons but same no. of protons.
Relative Atomic mass:
the mass of a single atom of an element relative to 1/12 mass of an atom of carbon-12.
Relative isotopic mass:
the mass of a single isotope of an element relative to 1/12 mass
of an atom of carbon-12.
3.1.1
What are the uses of time-of-flight (ToF) Mass Spectrometer?
- used to identify elements
- used to identify elements
- detecting illegal drugs
- forensic science
- space exploration
- carbon-14 dating
3.1.1
ToF MS stage 1 - Ionisation (Electrospray & Electron Impact) What happens?
Electrospray ionisation:
- The sample is dissolved in a volatile solvent and injected through a fine hypodermic needle (Very fine needle) giving a fine mist.
- A high voltage is applied to the tip of the needle, causing each particle to gain a proton as it leaves the needle.
- The solvent evaporates (and is therefore removed) producing gaseous, positive ions
- Equation = x + H+ –> xH+
Electron impact ionisation:
- The sample is vaporised
- an ‘electron gun’ (which is just an exposed filament of wire) is used to fire high energy electrons at the sample.
- This knocks one electron off each particle, so they become +1 ions.
- Has to be in gaseous state
- Equation = x(g) –> x+(g) + e-
3.1.1
ToF MS stage 2 - Acceleration What happens?
- An electric field is applied to give all the ions with the same charge a constant kinetic energy.
- As KE = 0.5mv2, Kinetic energy of the ions only depends on the mass (m) of the particles and their velocity (V).
- As all particles are given the same KE, heavier particles (larger Mr with a bigger m) move more slowly than lighter particles.
3.1.1
ToF MS stage 3 - Ion drift what happens?
- The ions enter a region with no electric field called the flight tube.
- Here the ions are separated based on their different velocities; the heavier ions have less KE (Move less quickly) compared to the smaller ions (which travel quicker) and arrive at the detector first.
- Equation (used to workout length of ion drift section) = velocity = d/t
3.1.1
ToF MS stage 4 - Ion detection What happens?
- The detector records the different flight times of the ions. The positively charged ions arrive at the negatively charged plate on detector and gain an electron, inducing a current in the detector and also becoming an atom again
- It’s important to know that the more abundant a given Ion is, the larger the current it induces. This means a bigger peak in the spectrum - he abundance of ions is proportional to size of current
3.1.1
General information about a Mass Spectrum (graph produced from MS)
This is what the machine gives you after those four Stages. It’s a series of peaks on a graph. The vertical axis is relative abundance and the horizontal axis is the m/z (Mass / Charge)
The relative abundance is a measure of how many of each ion is present. Often the highest peak (known as the base peak) is given a value of 100 and the other peaks are worked out relative to this value.
The m/z for a single charge ion = mass of the ion, as mass divided by 1 = mass. The m/z values for isotopes of an element are the relative isotopic masses for these isotopes.
3.1.1
What is an Electron Configuration, how does it work?
Principle energy levels = shells.
Basic information
* 1st energy level (moving out of nucleus) is called n=1; 2nd n=2 etc. This no. is called the principal quantum number.
* The energy levels get closer together as you move further from the nucleus. Distance between n=1 and n=2 is larger than the distance
between n=2 and n=3. This cont. further from the nucleus.
* Each energy level is divided into sub-shells: contains an orbital or a combination of orbitals.
* Orbital: a 3-D space + each orbital can hold up to 2 electrons.
* 2 electrons in the same orbital spin in opp. directions to minimise repulsions.
3.1.1
What is the Aufbau Principle?
It states that the lowest energy sub-levels are occupied first
1s
2s 2p
3s 3p 3d So, the order is: 1s 2s 2p 3s 3p 4s 3d 4p
4s 4p …
3.1.1
How can electron configurations be shortened?
Noble gas symbols in square brackets, such as [Ar], are sometimes used as shorthand in electron configurations
E.g. calcium (1s22s22p63s23p64s2) can be written as [Ar]4s2, where [Ar] = 1s22s22p63s23p6
3.1.1
A typical sub-shell diagram
- 4s sub-shell is at a lower energy level than the 3d sub-shell ∴ 4s fills before 3d.
- The electrons are indicated by ↿ and ⇂. They represent the different directions of spin
When electrons are in their lowest possible energy levels, the atom is said to be in the ground state.
Electrons repel each other, so will only form pairs in an orbital when they have to
3.1.1
What are Ionisation Energies?
The electrons in atoms and ions are attracted to the positive nucleus. Energy is required to overcome this attraction and remove electrons. Ionisation is the process of removing electrons
First ionisation energy: energy required to remove 1 mole of electrons from 1 mole of gaseous atoms, forming 1 mole of gaseous ions with a charge of +1.
- Successive ionisations give the 1st, 2nd, 3rd, etc. ionisation energies. Only 1 mole of electrons is removed with each ionisation.
Measured in kJmol-1. All ionisation energy values will be +ve as they are endothermic as energy is required to remove an electron from the attractive power of the nucleus.
The higher the value, the more energy is required to remove 1 mole of electrons.
3.1.1
Using successive ionisation energies
The existence of energy levels is proven by the large gaps in the successive ionisation energies as these correspond to the removal of electrons from energy levels closer to the nucleus + so more energy is required to remove the electron.
Successive ionisation energies are an indicator of the group to which an element belongs.
3.1.1
Explain trends in ionisation energies
The patterns in ionisation energies can be explained by the electronic structures of the atoms. 3 main factors which can be used to explain these patterns are…
…Atomic radius
* Atomic radius ↑ down a group + ↓ across a period.
* The further an outer electron is from the attractive power of the nucleus the less energy required to ionise it.
…Nuclear charge
* The greater the no. of protons, the greater the nuclear charge.
* A greater nuclear charge leads to a stronger attraction to the outer electron, so more energy is required to ionise it.
…Shielding by inner electrons
* The attractive power of the nucleus can be shielded by inner electrons.
* The more inner electrons there are, the more the nucleus is shielded + the less energy is required to ionise the outer electron.
3.1.1
Why does the first ionisation energy decreases down a group?
- Atomic radius ↑ - outer electrons are further away from the nucleus (at higher energy levels), so held less strongly by nucleus.
- Shielding from nuclear charge by inner electrons ↑
- Less energy required to remove the electrons ∴ 1st ionisation energy ↓
3.1.1
Why does the first ionisation energy increases across a period?
- Atomic radius ↓- outer electrons are closer to the nucleus (at lower energy levels), so held more strongly by nucleus.
- Nuclear charge ↑
- Shielding by inner electrons is the same (as outer electron is in the same energy level).
- More energy required to remove the electrons ∴ 1st ionisation energy ↑
3.1.1
Why is the 1st ionisation energy lower than expected for elements in Group 3 and Group 6
Atoms of elements in group 3 and 6 show a lower 1st ionisation energy than would be expected. This gives us evidence that 2nd + 3rd energy levels are divided into 2 sub-shells, the 1st taking 2 electrons and the
2nd taking 6, ∴ proving sub-shells exist.
* Group 3 electrons have an s2p1 arrangement - Outer p1 electron is further from the nucleus. - Inner s2 electrons ↑ shielding so less energy is required to ionise the outer p1 electron
- ∴ 1st ionisation energy ↓
* Group 6 atoms have a p4 arrangement - The repulsion of 2 electrons in the same p orbital leads to less energy being required to ionise the outer electron.
- ∴ 1st ionisation energy ↓
3.1.1
Ionisation Energy in Group 1 and Group 0 elements
- Atoms of group 1 elements have the lowest 1st ionisation energy in every period as they have the greatest atomic radius + the lowest nuclear charge in a particular period.
- Atoms of group 0 elements have the highest 1st ionisation energy in every period as they have the smallest atomic radius + the highest nuclear charge in a period.
3.1.1
What are the Patterns in second ionisation energies?
Patterns in 1st ionisation energies are shifted one to the left when the patterns of 2nd ionisation energies are considered. Where a group 1 element would have the lowest 1st ionisation energy, it would have the highest 2nd ionisation energy.
- Group 1 elements have the highest 2nd ionisation energy in a particular period as the 2nd electron is being removed from an energy level closer to the nucleus. Group 2 elements have the lowest 2nd ionisation energy in a particular period
3.1.2
Relative Atomic Mass and Relative Molecular Mass
Relative atomic mass (Ar): the average mass of an atom of an element relative to 1/12 the mass of an atom of carbon-12.(Unit: none)
Relative atomic mass (Mr): the average mass of an atom of a molecule relative to 1/12 the mass of an atom of carbon-12.(Unit: none)
3.1.2
The following all have the same numerical value:
- Relative molecular mass (Mr): the average mass of a molecule relative to 1/12 the mass of an atom of carbon-12 (carbon was chosen as it is a solid at room temp., non-toxic, and easy to separate).(Unit: none)
- Relative formula mass (RFM) may be used for ionic compounds but Mr is accepted for all compounds. (Unit: none)
- Molar mass: the mass of 1 mole. (Unit: gmol-1)
3.1.2
The Mole and the Avogadro Constant
Avogadro constant: the no. of particles in one mole = 6.02 x 1023
So, for solids and pure liquids (not solutions): mass/Ar = moles =
number of particles in Avogadro’s constant
3.1.2
Calculating Masses in Reactions
1) Calculate the number of moles of the species with enough data to do this.
2) Use stoichiometry of the equation to deduce the number. of moles of target species (the one we are being asked about).
3) Convert moles of target species to the mass.
3.1.2
The Ideal Gas Equation
The ideal gas equation is: pV = nRT, in this equation:
* p = pressure (1atm = 101325Pa = 101325Nm-2) (Unit: Pa)
* V = volume (1m3 = 1,000dm3 = 1,000,000cm3) (Unit: m3)
* n = no. of moles (k = kilo = x1,000; M = mega = x1,000,000) (Unit: mol)
* R = gas constant = 8.31JK-1 mol-1
* T = temperature (K = °C + 273; °C = K - 273) (Unit: K)
3.1.2
define: Empirical and Molecular Formula
- Empirical formula: the simplest whole no. ratio of atoms of each element in a compound.
- Molecular formula: the actual no. of atoms of each element in a compound.
- Molecular formulae are simple whole no. multiples of empirical formulae.
3.1.2
Calculating Empirical Formula
1) Convert masses to moles: moles = mass/Ar
2) Divide each molar quantity by the smallest.
3) If one of the numbers are not close enough to round (not close enough to whole by 2 d.p.)multiply it by a factor accordingly.
3.1.2
Ionic Equations
Some chemical reactions (ones involving ionic compounds) are reactions between only some of the ions involved in a reaction. The balanced equation can be rewritten as an ionic equation leaving out the ions which do not take part in the reaction (Those non-partakers are called spectator ions)
3.1.2
What is Percentage Yield?
- how is it calculated
- which one is smaller and why ( actual or theoretical)
Percentage yield: the percentage of the theoretical yield which is achieved in the reaction.
* % yield = actual yield/theoretical yield x 100%
- Theoretical yield: the amount of product that we expect to obtain based on our calculations.
- Actual yield: the true amount of product obtained.
–> Actual yield is less than the theoretical yield because:
* loss by mechanical transfer (transferring from one container to another)
* loss during a separating technique, e.g. filtration
* side reactions occurring
* reaction not being complete
3.1.2
What is Atom Economy?
Atom economy: a measure of how efficiently the atoms in the reactants are used in a chemical reaction. It can be calculated as a % using the following equation: % atom economy = Mr of desired product/sum of Mr of all reactants x 100%
3.1.2
Concentrations
concentration = moles of solute/volume of solution (dm3)
This means: moles = [ ] x vol (dm3)
(The units of [ ] are moldm-3 - also written as M - and gdm-3)
3.1.2
Calculations Involving Gases
✴ Avogadro’s hypothesis: Equal volumes of any gas measured at the same temp and pressure contain the same number of moles of gas.
Molar volume: the vol. of 1 mole of gas under the conditions of the reaction. moles = volume/molar volume (mol. = V/Vm)
–> standard conditions
1) Standard Temperature and Pressure (STP), Vm = 22.4dm3 (273K (0°C), 1atm)
2) Room Temperature and Pressure (RTP), Vm = 24.0dm3
(298K (25°C), 1atm)
3.1.3
What is Melting?
The change of state from solid to liquid. Temperature that this occurs = the melting point m.p.)
* Energy is taken in when a substance melts to overcome bonds or intermolecular forces. The stronger the forces or bonds in a substance, the greater the energy required to melt the substance.
3.1.3
What is Freezing?
change of state from liquid to solid. Temperature that this occurs = the melting point also
* Energy is released when a substance freezes as forces or bonds are formed. The stronger the forces or bonds formed on freezing, the more energy is released.
3.1.3
What is Boiling?
Change of state from liquid to gas. Temperature that this occurs = the boiling point (b.p.)
* Energy is taken in when a substance boils. The stronger the bonds or intermolecular forces in a liquid substance, the greater the energy required to boil the substance.
3.1.3
What is Condensing?
change of state from gas to liquid. Temperature that this occurs = The boiling point (b.p.)
* Energy is released when a substance condenses. The stronger the bonds or forces formed on condensing, the more energy is released.
3.1.3
What is Subliming / sublimating?
Change of state from solid to gas on heating; change of state from gas to solid on cooling.
* Substances which sublime for the A-Level = solid iodine and solid carbon dioxide (solid carbon dioxide is known as ‘dry ice’)
3.1.3
What is Ionic Bonding?
The electrostatic attraction between oppositely charged ions in an ionic lattice. These ions are formed by electrons being
transferred from one atom to another.
3.1.3
What are the formulars of the 5 compound ions?
Formulae of Compound Ions:
Ammonium: NH4+
Carbonate: CO3 2-
Hydroxide: OH-
Nitrate: NO3-
Sulfate: SO4 2-
3.1.3
What is a Giant Ionic Structure?
- Properties?
1) Particles of the 3-D lattice are cations & anions.
2) Strong electrostatic attractions hold cations & anions together.
Ionic compounds are hard, because the anions & cations are strongly attracted to each other therefore difficult to separate - but if force is applied and lattice shifts, same charges will repel
3.1.3
What are the Melting + Boiling Points of giant ionic lattices?
The giant ionic lattices are held together by a large number of strong electrostatic attractions between oppositely charged ions. Therefore, large amount of energy required to overcome the forces. That means ionic compounds tend to have high b.p.’s and m.p.s
* Importantly, the smaller the ions (in terms of actual size) and the higher the charge on the ions, the stronger the ionic bond.
3.1.3
What is the rules of general Electrical Conductivity?
To conduct electricity, they must:
1. The substance must contain charged particles.
2. The charged particles must be free to move throughout the substance.
3.1.3
Do ionic lattices conduct electricity?
Ions are charged particles. BUT, they are fixed in positions in the lattice by strong ionic bond. This means ionic compounds do not conduct in solid state.
* In molten state, or in an aqueous solution, the ions are free to move. So the solution containing the ions, e.g. salt water (NaCl in H2O), will conduct.
3.1.3
Explain ionic lattice solubility
- Ionic compounds are polar molecules, this means they tend to dissolve in polar solvents, such as water
- When moving water molecules hit an ionic lattice, they can knock ions off the outer layers
- The water molecules then surround the ions, causing the substance to break up and dissolve
3.1.3
What is Covalent Bonding?
The electrostatic attraction between a bonding pair of electrons and the nuclei of the 2 atoms involved in the bond.
* Atoms make 1 covalent bond for each electron that it needs to get a ‘full’ shell.
3.1.3
What is a molecular covalent structure?
Give example…
1) Particles of the 3-D lattice are covalent
molecules.
2) The forces between the molecules are weak van der Waals forces.
- for example I2 (Iodine)
3.1.3
- Hardness
- Melting / Boiling Points of a molecular covalent structure
- Relatively soft as they do not have strong intermolecular forces.
- Relatively low because the van der Waals forces between the molecules are weak. This means it only takes a little energy required to overcome them.
3.1.3
- Solubility
- Electrical Conductivity
of a molecular covalent structure
- They’ll dissolve in non polar solvents, because they themselves are not polar. This means they will not dissolve in water. Your typical solvent will be some non-polar organic substances.
- Covalent things do not conduct electricity; covalent things don’t contain any charged particles which are free to move.
3.1.3
What is a Macromolecular (Giant Covalent) Structure?
Give examples…
1) The atoms are held together by strong covalent bonds in a giant network.
- for example diamond and graphite
3.1.3
- Hardness
- Melting / Boiling Points of a Macromolecular (Giant Covalent) Structure
- Very hard due to many strong covalent bonds + rigid 3-D structure holding surface atoms in place.
- You need very high temperatures to melt and boil giant covalent things. This is because ALL the strong covalent bonds holding the giant lattice have to be broken which needs a lot of energy. Compare this to simple covalent structures, where only VDW’s or Dipole Dipole IMF’s have to be broken and you quickly see why the M.P./B.P’s are so different
3.1.3
- Solubility
- Electrical Conductivity
of a Macromolecular (Giant Covalent) Structure
- These lot are insoluble. All the strong covalent bonds of the giant covalent structure need to be broken to free the atoms and let them move through the solvent.
- There are no charged particles, since the lattice particles are atoms, so giant covalent crystals are insulators. Graphite is an exception to this rule because it has a ‘spare electron’. It doesn’t really break the rule as an electron IS a charged particle and in graphite’s case, it can move!
3.1.3
What is Metallic bonding?
It is the electrostatic attraction between metal cations (metal positive ions, cat means +) delocalised electrons in a lattice
3.1.3
What is a metallic structure?
1) Particles of the 3-D lattice are positive ions surrounded by a ‘sea’ of delocalised electrons.
2) The positive ions are held together by metallic bonding; metallic bonding literally is the electrostatic attraction between metal cations and the associated delocalised electrons.
3.1.3
Metallic structure
- Hardness
- Solubility
- Metals are typically hard, due to strong electrostatic attraction between metal cations and delocalised electrons.
- Metals are Insoluble, except in other liquid metals. This is, again, because of the strength of metallic bonds
3.1.3
Metallic structure
- Melting + Boiling Points
Metals have relatively high M.P./B.P. because there are strong forces of attraction between cations and delocalised electrons
* The greater the number of delocalised electrons per atom, the stronger the metallic bond so therefore the higher the m.p./ b.p.
* The smaller the ions in the metallic lattice, the stronger the attraction between the delocalised electrons + the cations therefore the higher the m.p./b.p.
* Transition metals have much higher m.p./b.p. than the main group metals (group 1 and 2) due to the large number of d sub-shell electrons. These electrons may become delocalised, creating an even stronger metallic bond.
* This principle : smaller ion + more charge = stronger bond is the same as the ionic bonding principle
3.1.3
Metallic structure
- Conductivity
- Metals have delocalised electrons in their structures, these can move. An electric current = the movement of charged particles.
- Heat is conducted when particles can move and are close enough together to pass the heat energy from one to another. The delocalised electrons enable heat energy to be passed through the metal because they’re nice and close. So metals are good conductor of heat.
3.1.3
Metallic structure
- Malleable + Ductile
- Because of the layered structure of the lattice, metallic layers can slide over each other without disrupting the bonding. This makes metals malleable
- They’re also ductile (this means you can draw them out into a wire)
3.1.3
What is an alloy?
- An Alloy is simply a mixture of metals.
- Alloy’s aren’t malleable because different metals are different in size
- This makes the structure of an Alloy irregular, so it is much more difficult for layers to slide.
3.1.3
What do shapes of Simple Molecules and Ions depend on?
- The shapes of a covalent molecule or ion depends on the repulsion of the electrons around a central atom.
- The electron pairs are charge clouds, areas where you have a big chance of finding an electron around an atom that repel each other.
3.1.3
What are the 2 types of electron pairs?
There are 2 types of electron pairs:
* Bonding pairs: pairs of electrons which are shared in covalent bonds.
* Lone (non-bonding) pairs: pairs of electrons which are unshared.
3.1.3
Explain the Valence Shell Electron Repulsion Theory
✴ Pairs of electrons in the outer shell of atoms arrange themselves as far apart as possible to minimise repulsion.
✴ Lone pairs are held closer to the central atom so they have a greater repulsive effect on the other pairs of electrons.
- This means lp–lp repulsion is greater than lp–bp repulsion, which is greater than bp–bp repulsion.
3.1.3
Shapes of Molecules
- What occurs?
- What determines the molecules’ shape?
The molecule or ion will take up a shape which minimises electron pair repulsions. The shape of the molecule is determined from:
* The total amount of electron pairs around a central atom.
* The amount of (sets of) bonding pairs of electrons.
* The amount of lone pairs of electrons.
3.1.3
Describe all of the 5 shapes without any lone pairs
- Linear ; BP=2, LP=0, BA= 180
- Trigonal planar ; BP=3, LP=0, BA=120
- Tetrahedral ; BP=4, LP=0, BA= 109.5
- Trigonal Bipyramidal ; BP=5, LP=0, BA= 90 + 120
- Octahedral ; BP=6, LP=0, BA= 90
3.1.3
Describe all of the 4 shapes with lone pairs
- Pyramidal ; BP=3, LP=1, BA= 107
- Bent ; BP=2, LP=2, BA= 104.5
- Trigonal planar ; BP=3, LP=2, BA= 120
- Square planar ; BP=4, LP=2, BA= 90
3.1.3
What are Intermolecular forces?
Where do they exist?
These are forces that DON’T require the exchange of an electron. They exist because of bonds, they aren’t bonds themselves. They exist between molecule.
3.1.3
What is Electronegativity?
How is it measured?
The measure of attraction by an atom to a pair of electrons in a covalent bond.
* Electronegativity is measured on the Pauling Electronegativity Scale. A higher number on the scale means an element is better able to attract the bonding electrons in a covalent bonds; a higher number means it likes electrons more.
3.1.3
What 3 factors does electronegativity depend on?
1) The distance of the bonding electrons from the attractive power of the nucleus (atomic radius).
2) The size of the nuclear charge (i.e. atomic no.).
3) The attractive power of the nucleus being shielded by inner electrons - shielding
3.1.3
Electronegativity across a period…
INCREASES. This is because…
* atomic radius goes down across a period, giving a progressively stronger attraction between the positive nucleus and the 2 electrons in the covalent bond.
* nuclear charge goes up across a period. This will cause a greater attraction for the electrons in the covalent bond.
3.1.3
Electronegativity down a group…
DECREASES. This is because:
* atomic radius goes up down a group, giving a progressively weaker attraction between the positive nucleus and the electrons in the covalent bond.
* shielding of the nuclear charge increases down a group as there are more electrons in inner energy levels.
3.1.3
What is a non-polar covalent bond?
The electronegativities of the 2 atoms in the covalent bond are the same. This means that the bonding pair of electrons are shared equally, i.e. electron distribution is symmetrical. E.g. H-H, O=O etc.
3.1.3
What is a polar covalent bond?
One atom is more electronegative than the other. The electrons in the covalent bond will therefore be closer to one atom than the other, i.e. electron distribution is unsymmetrical. This means one atom will be partially positive and the
other partially negative. E.g. H-Cl, C-Cl, Be-Cl, C=O, etc.
3.1.3
What is a dipole?
It is a difference in electronegativity between 2 atoms caused by a shift in electron density in the bond.
3.1.3
What occurs in polar bonds?
- In a polar bond, the difference in electronegativity between the 2 atoms causes a dipole.
- If charge is distributed unevenly over a whole molecule, then the molecule will have a permanent dipole. Molecules that have permanent dipoles = polar molecules. Whether or not a molecule is polar depends on whether it has any polar bonds + its overall shape.