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# Energy matters

Unit 1 Energy matters • Speed of reaction (rate) and factors affecting speed of reaction Concentration • Temperature • Particle size • Catalyst • [Provision of "STARTING" energy] • Collision Theory Collision theory says that reactions cannot happen unless reactant particles come in contact. Because particles move quickly this contact is usually a high velocity collision. Just before the collision both particles will have high kinetic energy. At the moment of collision KE = 0 instead this energy is absorbed into the bonds (PE ,Chemical Energy, Enthalpy). It shows its self as increased vibration of the atoms in the bond if the increase is big enough the bond breaks and a new bond or bonds can form. I f the energy absorbed on impact is not enough to cause the bond to break the particles will rebound unchanged [soft collision] This means that there must be a minimum amount of collision energy for a reaction to happen Activation Energy [see enthalpy later on] Application of collision theory -Concentration If the concentration of a reactant increases that means there are more particles in unit volume. In turn the number of collisions must increase just because of the particle density. P article density is the number/fraction of successful collisions will be the same ratio. hence the rate increases as the concentration increases -Surface Area 1. A substance/mixture/in which everything is in the same state of matter is said to be Homogeneous. 2. A substance with two or more states of matter present is said to be Heterogeneous. Surface area is a consideration in heterogeneous reactions usually with one reactant being solid. In this case the reaction must happen on the solid surface. When the surface area is increased (smaller particles) the number of collisions between solid particles and the other reactant will also increase. Surface area increases reaction rate increases

-Temperature Temperature is a measure of the average energy of particles in a system. . In other words reaction rate increases much more than directly with increasing temperature. At a given temperature (T1) the energy dispordution in a reacting system will follow the usual statistical disprodution (normal). This relates to the absolute (Kelvin) temperature scale where all particle movement ceases at 0K. This shows that a small 10K increase in temperature for example can lead to a large increase in the number of successful collisions. T1 Average energy Activation energy Number of particles Succsesful Collisions at T1 Ea Average energy Succsesful collisions at T2 Catalysts 29 September 2010 19:57 Definition: A catalyst is a substance which speeds up a reaction with out itself being used up. As a rule of thumb reaction rate doubles with every 10 degree rise in temperature.

Linier and angle of collision matters.Heterogeneous Catalyst : A different state of matter (usually solid) from the reactants Catalys Reaction/process t Ni Hardening of oil to form margarine (Hydrogenation) Pt & Pd Catalytic Converter Al2O3 Fe Pt V2O5 Cracking Haber Process (NH3) Ostwald Process (HNO3) Contact Process (H2SO4) How do Heterogeneous catalysts work? The catalyst surface has active sties to which the reactant particles adsorbed.g. Adsorption would very much favour geometry a) so rate is improved. As a result of the particle bonds existing bonds in the reactant particles will weaken this means that the necessary collision energy (EA) for complete bond breaking is now lowered. Collision Geometry It should not be assumed that all reacting particles are spheres instead there are definite shapes. . Local increase in concentration: At the active sites the reactions will be considerably closer than when not adsorbed. E. This reduction in activation energy means that more collisions will be successful and reaction rate goes up. There are also two ather ways in which adsorption can lead to faster reaction.

Parallel geometry Perpendicular geometry Graphs Exstent of reaction CaCO3 + HCl CaCO3 + 2HCl ----> CaCl2 + H2O + CO2 (g) 1mol 2mol 1mol 100g 44g 1g 0.44g A B A B Powder Lumps .

810s [see note book for table] b. Mg + 2HCl ---> MgCl2 + H2 (g) How how much fast Enthalpy Defined as the energy content in the bonds of systems shown as H. It is a STATE FUNCTION (change ∆H) depends only on statring and finnshing positions NOT on the path taken. Rate of reaction from the graphs a. Path of a reaction .Each of the two graphs can be split into two parts A and B. The same but Mg ribbon 2. Part A gives information on the initial speed of reaction. Part B gives information on how much reaction has occurred when the line levels off the reaction is complete. The steeper the line the faster the reaction. Average rate On the CaCO3 (lumps) reaction graph work out the average reaction (gs-1) during the period of 90 . Reaction rate at a given time Calculate the reaction rate at t=450s [see note book for table] Graphs and Enthalpy 29 September 2010 21:37 Mg + 2HCl ---> MgCl2 + H2 (g) 1mol 2mol 1mol 24g INXS 24000cm3 0.024g 24cm3 Vol of H2 Changes 1. The same but Zn lump (same number of moles) 3.

EA (reverse) Presence of Catalyst . ∆H=EA(forward) .The enthalpy change (∆H) in a reaction is comomly shown on a diagram. E. A+B ----> C+D Reactants Products ∆H =H2+H2 ∆H = -VE (exothermic) E.g. Activation energy (reverse) is different. This means that exothermic changes to endothermic. A+B ----> C+D Reactants Products ∆H =H2-H2 ∆H = +VE (endothermic) Reverse reactions A reaction can reverse C+D ---> A+B when this happens the magnitude of ∆H stays the same but its sign changes.g.

E.+ H2O Omit spectator ions H+(aq) + OH-(aq) ---> H2O(l) Neutralisation is just the formation of water ∆HNEUTRAL = -56kJmole-1 of water formed Enthalpy of Solution This is the heat energy change when one mole of a substance dissolves completely in a solvent (usually water). NaCl ---> Na+(g) + Cl-(g) Lattice Enthalpy 2. Catalyst Reaction Pathway Enthalpy changes for specific reactions Enthalpy of combustion: Heat energy given out when 1 mole of a substance in its standard state (room temperature) and 1 atmosphere pressure burns completely.---> Na+Cl. Na+(g) + Cl-(g) --->Na+(aq) + Cl-(aq) Hydration 3.g.g. The dissolving process eg for NaCl actually occurs in two steps.+ Na+OH. Propane C3H8(g) + O2 ---> CO2(g) + H2O(l) ∆H -2220kJmole-1 Enthalpy of formation This is the heat energy change when one mole of a substance at standard conditions is formed form its elements at standard conditions.g. H2 (g) ---> H2 (g) ∆H = 0kJmole-1 Enthalpy of Neutralisation This is the heat energy given out when 1mole of acid (H+(aq) ) is exactly neutralised by one mole of alkali (OH-(aq)) H+Cl. E. 1.No Catalyst Enthalpy The Activation energy is reduced. 3C(s) + 4H2 (g) ---> C3H8 (g) ∆H = -104kJmole-1 The definition above covers the formation of elements E. ∆H is not changed. NaCl(s) ---> Na+(aq) + Cl-(aq) Dissolving Because enthalpy is a state function ∆H3 = ∆H1 + ∆H2 .

. Statistically this cannot happen. and equation tells us about what we start with (reactants) and end with (products).g. These steps do not all occur at the same speed. This concept applies to most reactions E.02x1023. It is now thought that reaction mechanisms consist of a series of two particle steps (collisions) which add up to give the overall reaction.g. The in excess does NOT effect how much reaction happens and is ignored in calculations. The number is caled Avogadro's constant (NA or L) its value is 6. It is known as the rate determining step (RDS). This is because that substance is not in the RDS. The left over reactant is said to be in excess (INXS).[Hesse's Law see unit 3] Reactions 05 October 2010 20:05 Reaction Mechanism The dissolving process above shows that a change can actually be the sum of several steps. There are some reactions where varying concentration of a particular reactant has no effect on reaction rate. [SEE NOTHE BOOK FOR INXS CALCULATIONS] The Mole and Avogadro 05 October 2010 20:58 The mole continued Avogadro established that one mole of any substance contains the same number of particles. But it tells nothing about what happens in between (the mechanism). E. 3Cu + 8HNO3 ---> 3Cu(NO3)2 + 2NO + 4H2O This equation might suggest that 11 particles need to collide at the same time for a reaction to happen. More often one reactant will completely be used up and some will remain of the other. [FOR REACTION CALCULATIONS SEE THE NOTE BOOK!] The idea of excess It is actually quite unusual for exactly the correct quantities of reactants to be available. The overall speed of a reaction is governed by the slowest.

and SiO2 Molecules have low MP and BP • Covalent Network are very high MP • and BP Never conduct (except carbon in the • form of graphite and a few specialized compounds) Fullerenes are molecular forms of • carbon from C60 upwards.1mole 1mole 1mole 1mole 1mole 1mole 1mole of of of of of of of He <---> 6. Separate molecules or atoms are • described as discrete (separate). O2 Compounds E. KNO3 Electrons transferred Same electron arrangement as nearest Rare gas . H2O Shared electrons (2 electrons shared = one bond) Same electron arrangement as nearest rare gas. Ionic • • • • Metal ---> Non-Metal Compounds only E.g.02x1023 Cl.02x1023 Atoms Molecules Atoms Formula Units* Ions Ions Ions *Because ionic compounds do not acctually contain particles of the whole sunstance a pretend particle unit called the formula unit is used.02x1023 Cl2 <---> 6.02x1023 Na+ <---> 6. B.g.<---> 6.02x1023 Cl2 <---> 2x6.g. This particle contains exactly a correct number of positive ions to make up a formula. • Si.02x1023 NaCl <---> 2x6. Molecules or covalent network C.02x1023 NaCl <---> 6. Bonding 05 October 2010 21:11 Covalent • • • • • Non-metal ---> Non-metal Elements E.

Fe Alloys E.d. solutions or melts do conduct as the lattice is broken down and the ions are free to move. • Van der Waals Forces (v. (100 on a strength scale) Other forms of bonding There are also some weaker types of bonds as well as the three strong ones. • • • Metallic Metal ---> Metal Elements E. • Do not have electron arrangements • Variable MP and BP • Always conduct (by electron movement) • • • • • All three of three forms of bonding are strong. Steel Delocalised electrons Electrostatic attraction between positive ions and delocalised electrons.g.Ions Ions have a high MP and BP Solids do not conduct.W) In any substance it must happen at one point (randomly) that • the electrons are unevenly disproduced with the majority in one area. Dipole charge separation • is set up represented by Temporary Positive Negative .g.

These two electrons can only be shared equally between two atoms if the atoms are the same or if the atoms have equal electrotivities [see data book page 10] E.Inside the molecules In many cases change in electronegativity (∆E) cannot = 0.g.W forces = instantaneous dipole to induce dipole attraction. Once it breaks down there can be similar occurrences elsewhere in the substance many times per second.This dipole by electrostatic attraction induce a similar dipole on nearby particles.g. The differance in attraction for the two bonding electrons can be ignored. C-H bond ∆E = 2.4 unequal sharing of bonding electrons results.Between the bonds Intramolecular . Al and Be E=1.3 0.5 Ca and Li E=1. This means that one atom gets more than 50% of the electrons and the other atom gets less than 50% E. E.4 aprox). For small ∆E values (≤0.g. The bond can still be considered to be covalent.2 = 0.0 C and S E=2.2. This attraction is short lived effect and can spread over a large number of particles . Summarise v.5 Intermolecular .3 ---> C-H bond is covalent If ∆E is greater than 0.5 .d. Permanent dipole to permanent dipole attractions Electronegativity (Linus Paulling) This concept refers to the attraction for the two shared electrons in a covalent bond. And the particles are held together weakly by electro static attraction. .

The permanent dipole shown (also called a polar bond) can attract other similar dipoles.g. In reality there is actually a spectrum of bonding running from covalent to ionic at the two ends with anything in between also being possiable.8 the charge seperation becomes to great that the two "atoms" actually become Ions and the bond is now refered to as Ionic.8 Polar covalent . <---> = electrostatic attraction The electro static attraction shown is an example of a permanent dipole to permanent dipole bond. E. If however ∆E >1. Polar bonding All bonds with ∆E >0. Covalent Ionic >1.4aprox are refered to as polar covalent (polar = charge seperation).