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########Topic 4.1KINETICSRate equationsDetermining orders of reactionExplaining
orders of reactionEffect of changing conditions on the rate constant##
RATE EQUATIONSThe relationship between the rate of a chemical reaction and the
concentration of the reactants is shown by the rate equation of the reaction.
Consider the reaction A + 3B ( 2C + 4DThe rate of this chemical reaction is given
by the equationRate = k[A]x[B]y[A] is the concentration of A, and [B] is the
concentration of B.x and y are the orders of reaction with respect to A and B
respectively. The order of reaction with respect to a given reactant is the power
of that reactant's concentration in the rate equation. ##The sum of these powers,
in this case x + y, is known as the overall order of reaction:The overall order of
reaction is the sum of the powers of the reactant concentrations in the rate
equation##k is the rate constant of the reaction.The rate constant is the constant
of proportionality in the rate equation. ##
Rate of reactionDuring a chemical reaction, the concentration of the reactants
decreases and the concentration of the products increases.#The rate of a reaction
is the decrease in concentration of reactants per unit time, or the increase in
concentration of products per unit time.##The units of rate of reaction are moldm-
3s-1.
DETERMINING ORDERS OF REACTION The orders of reaction with respect to each reactant
in the reaction can be determined by carrying out the reaction with various
different initial concentrations and measuring the change in initial rate of
reaction. The orders of reaction can be determined arithmetically or graphically.If
the order of reaction with respect to one reactant is being determined, the
concentration of one reactant only should change; the others should remain constant
so that the change in rate can be attributed to the change in concentration of that
reactant alone.If the overall order is being determined, the concentration of all
reactants should change by the same factor.1. The arithmetic method (used in Unit 4
examinations)(change in concentration)order of reaction = change in rateIf the
reaction is first order, then if the concentration doubles the rate will also
double. If the concentration triples the rate will also triple, etc.If the reaction
is second order, then if the concentration doubles the rate will quadruple. If the
concentration triples the rate will increase ninefold, etc.If the reaction is zero
order, then the change in concentration will have no effect on the rate of
reaction.Example 1Consider the reaction RX + OH- ( ROH + X-The following rate data
were obtained at constant temperature:Initial concentration of RX/ moldm-3#Initial
concentration of OH/ moldm-3#Initial rate/ moldm-3 s-1##0.01#0.04#8 x 10-
3##0.01#0.02#4 x 10-3##0.005#0.04#4 x 10-3##From expt 2 to expt 1, the
concentration of hydroxide ions doubles and the concentration of RX is unchanged.
The rate also doubles, so the order of reaction with respect to OH- is 1.From expt
3 to expt 1, the concentration of RX doubles and the concentration of hydroxide
ions is unchanged. The rate also doubles, so the order of reaction with respect to
RX is also 1.The rate equation can thus be written as follows: rate = k[RX][OH-]
Having deduced the rate equation, the rate constant can be calculated using the
data in one of the experiments. Eg in expt 1, k = rate/([RX][OH-]) = 8 x 10-3/(0.04
x 0.01) = 20 mol-1dm3s-1.Example 2Consider the reaction PCl3 + Cl2 ( PCl5The
following rate data were obtained at constant temperature:Initial concentration of
PCl3/ moldm-3#Initial concentration of Cl2/ moldm-3#Initial rate/ moldm-3 s-
1##0.2#0.1#0.0004##0.4#0.1#0.0008##0.8#0.2#0.0064##From expt 1 to expt 2, the
concentration of PCl3 doubles and the concentration of Cl2 is unchanged. The rate
also doubles, so the order of reaction with respect to PCl3 is 1.From experiment 2
to experiment 3, the concentration of both reactants doubles. The rate increases
eightfold, so the overall order of reaction is three.The order of reaction with
respect to chlorine is therefore 3 � 1 = 2.The rate equation can thus be written
as follows: rate = k[PCl][Cl]2So k = rate/[PCl3][Cl2]2 = 0.0004/(0.2 x 0.12) = 0.2
mol-2dm6s-1
2. Graphical method (used in practicals)If the concentrations in the different
experiments are not simple whole number ratios of each other, it is not easy to
compare the concentrations and rates. The order of reaction with respect to each
reactant can be deduced by plotting a graph of concentration vs initial rate.first-
order reactionsIf Rate = k[A], then a plot of initial rate against initial
concentration will be a staight line through the origin of gradient k:#second-order
reactionsIf rate = k[A] 2, then a plot of initial rate against initial
concentration will be a curve through the origin.#zero order reactionsIf rate = k,
then a plot of initial rate against initial concentration will be a horizontal
line:#An even better method is to plot log (rate of reaction) against log
(concentration). This should always give a straight line, the gradient of which is
the order of reaction.3. Measuring initial rates of reactionIn some reactions, it
is not easy to measure the rate of reaction directly, and easier to mention the
time taken for a particular stage in the reaction to be reached.Since rate is the
change in concentration per unit time, it follows that the rate is inversely
proportional to time taken. A graph of 1/t against initial concentration will give
curves like those shown above.Examples of such measurements could be:time taken for
fixed amount of gas to be producedtime taken for absorbance to change by a certain
amountuse of a clock reaction: the appearance of a certain coloured product is
delayed by adding a fixed amount of another species.Eg S2O82-(aq) + 2I-(aq)
( 2SO42-(aq) + I2(aq)Iodine is produced in this reaction. If starch was added to
the original mixture, a blue-black colour would appear immediately. However if a
fixed amount (ie 0.02 moles) of sodium thiosulphate is also added to the mixture,
it reacts with the iodine and a blue-black colour is only seen when all the
thiosulphate has been used up.It is possible to measure the time taken for the
blue-black colour to appear.
EXPLAINING ORDERS OF REACTIONThe orders of reaction for a chemical equation are not
always the same as the reaction coefficients:Eg the reaction NO2 + H2 ( NO + H2O
has the following rate equation:rate = k[NO2]2It is therefore not possible to
predict the rate equation of a reaction simply by looking at the reaction
coefficients.Many reactions consist of a series of different steps, some of which
are slow and some of which are very fast.It is the slowest step in a chemical
reaction which determines how fast a reaction is. For this reason the slowest step
in a chemical reaction is called the rate-determining step. Changing the rate of
this step will affect the overall rate of reaction; changing the rate of fast steps
won�t.Eg consider the reaction NO2 + H2 ( NO + H2OThis reaction happens in two
steps:Step 1: NO2 + NO2 ( NO3 + NO this step is slowStep 2: NO3 + H2 ( NO2 + H2O
this step is fastStep 1 is the slowest step and is therefore the rate-
determining step. This involves two molecules of NO2, and so doubling the
concentration of NO2 will make collisions in this step four times more likely. So
the reaction is second order with respect to NO2. H2 is not involved in this step;
it is only involved in the second, fast step. Changing the concentration of H2
therefore has no effect on the rate of reaction, and the reaction is zero order
with respect to H2.The rate equation of a chemical reaction is determined by the
number of each species involved in the rate-determining step of that reaction.
EFFECT OF CHANGING CONDITIONS ON THE RATE CONSTANTThe rate equation shows the
relationship between the concentration of reactants and the rate of reaction.If the
concentration of one of the reactants increases, the rate of reaction will also
increase, the rate constant, k will not change.If the pressure increases, the
concentration of all the reactants will increase and so the rate of reaction will
also increases. Again the rate constant will not change.The rate constant k is thus
independent of concentration and pressure.If the temperature increases, however, or
a catalyst is added, the rate of reaction increases without a change in
concentration, and so it must be the rate constant, k, that is changing.The rate
constant k thus varies with temperature, and is also affected by the addition of a
catalyst.If the temperature is increased, the rate constant k also increases.If the
temperature is decreased, the rate constant k will decrease.If the concentration or
pressure is changed at constant temperature, the rate constant will not change.
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########AP Chemistry Chapters 8 & 9 � Bonding Study GuideStudents should be
able to... Define: #HYPERLINK "http://www.nettrekker.com/subj ect/?
ctgry_id=X101999"##chemical bond#, #HYPERLINK "http://www.nettrekker.com/subj ect/?
ctgry_id=X102076"##ionic#, #HYPERLINK "http://www.nettrekker.com/subj ect/?
ctgry_id=X102070"##covalent#, metallic, #HYPERLINK
"http://dl.clackamas.cc.or.us/ch104-08/elements.htm"##diatomic#, #HYPERLINK
"http://www.nettrekker.com/results/?ctgry_id=X102073"##polar#, #HYPERLINK
"http://www.nettrekker.com/results/?ctgry_id=X102074"##nonpolar#, and #HYPERLINK
"http://www.nettrekker.com/results/?ctgry_id=X102096"##VSEPR# Use #HYPERLINK
"http://www.nettrekker.com/results/?ctgry_id=X102083"##electronegativity# to
determine the type of bond formed between two elements Calculate bond energies.
Determine the polarity of a dipole. Draw #HYPERLINK
"http://www.nettrekker.com/results/?ctgry_id=X102090"##Lewis structures# for
covalent molecules, including double and triple bonds. Draw #HYPERLINK
"http://www.nettrekker.com/results/?ctgry_id=X102090"##Lewis structures# for
polyatomic ions Use #HYPERLINK "http://www.nettrekker.com/results/?
ctgry_id=X102084"##formal charge# to determine the best #HYPERLINK
"http://www.nettrekker.com/results/?ctgry_id=X102090"##Lewis structure# Use
#HYPERLINK "http://www.nettrekker.com/results/?ctgry_id=X102096"##VSEPR# chart to
determine electron arrangement and molecular geometry. Use #HYPERLINK
"http://www.nettrekker.com/results/?ctgry_id=X102096"##VSEPR# chart to write
#HYPERLINK "http://www.nettrekker.com/results/?ctgry_id=X102090"##Lewis structures#
that include bond angles. Be able to draw resonance structures for covalent
molecules Calculate the enthalpy of formation, lattice energy, and associated
information.Determine hybridization of orbitals within a molecule (no sp3d or
sp3d2)Identify sigma and pi bondsSample AP Problems from Bonding:Questions 8-10
refer to the following diatomic species.(A) Li2#(B) B2#(C) N2#(D) O2#(E) F2 8. Has
the largest bond-dissociation energy9. Has a bond order of 210. Contains 1 sigma
(s) and 2 pi (p) bonds15. In a molecule in which the central atom exhibits sp3d2
hybrid orbitals, the electron pairs are directed toward the corners of(A) a
tetrahedron#(B) a square-based pyramid#(C) a trigonal bipyramid#(D) a square#(E) an
octahedron 17. The Lewis dot structure of which of the following molecules shows
only one unshared pair of valence electron?(A) Cl2#(B) N2#(C) NH3#(D) CCl4#(E) H2O2
47. CCl4, CO2, PCl3, PCl5, SF6 Which of the following does not describe any of the
molecules above?(A) Linear#(B) Octahedral#(C) Square planar#(D) Tetrahedral#(E)
Trigonal pyramidal Free response:5) Consider the molecules PF3 and PF5. a) Draw the
Lewis electron-dot structures for PF3 and PF5 and predict the molecular geometry of
each. b) Is the PF3 molecular polar, or is it nonpolar? Explain. c) On the basis of
bonding principles, predict whether each of the following compounds exists. In each
case, explain your prediction. (i) NF5#(ii) AsF5
Answers to Sample AP Problems:Multiple choice: 8) C 9) D 10) C 15) E
17) C 47. CFree Response: 5)##PRIVATE### INCLUDEPICTURE "C:\\Documents
and Settings\\user\\Local Settings\\Temp\\PF3.GIF" \* MERGEFORMAT \d ###(Trigonal)
pyramid(al) ### INCLUDEPICTURE "C:\\Documents and Settings\\user\\Local
Settings\\Temp\\PF5.GIF" \* MERGEFORMAT \d ####(Trigonal) bipyramid(al) ##1 point
for each structure Note ; One point (total) deducted if lone pairs not shown on F
atoms in either molecule. (b) The PF3 molecule is polar The three P-F dipoles do
not cancel, or, the lone pair on P leads to asymmetrical distribution of charge.
Note; "Molecule is not symmetrical" does not earn point. Both points can be earned
if answer is consistent with incorrect (a). (c) NF5 does not exist because no 2d
orbitals exist for use in bonding, or, N is too small to accommodate 5 bonding
pairs AsF5 does exist because 4d orbitals are available for use in bonding, or, As
can accommodate an expanded octet using d orbitals Note; Response with two correct
predictions with no explanations earns one point. Also, argument of "no expanded
octet" vs. "expanded octet" alone does not earn explanation point.
AP Chemistry � Chapter 8, Bonding FAQQ: How do s and p use d electrons in
expanded octets if they don � t have d electrons?A: Even though sulfur and
phosphorous do not have d electrons, there is still an empty d orbital present
(3d). While it is unusual, electrons can be shared in those empty d orbitals to
form expanded octets.Q: How do I know which bond is more polar without using an
electronegativity table?A: Use the periodic trend for electronegativity. The
higher electronegativity is the one furthest up and right on the periodic table.
To find the highest polarity, find the two elements that have the largest
difference in electronegativity (the furthest apart from each other on the periodic
table).Q: How do bond energies work?A: The bond energies obtained by breaking all
the bonds in the reactants (left side of the arrow) minus all the energy needed to
form bonds (on the right side of the arrow) would equal the net change in energy.
If there are coefficients, be sure to multiply the bond energy of the molecule by
the number of moles of that molecule present.Q: What do I do if I get a tie
between two different structures when evaluating formal charge?A: First, keep in
mind that the � true � structure is an average of all the possible structures. If
one of the structures IS the average of all the structures, then it must be the
best one. (Example: two double bonds, a triple bond and a single bond, and a
single bond and a triple bond would average out to two double bonds.) If that
doesn � t break the tie, then go with the structure that would best suit the
element � s charge. (Example: If it � s between C and O having a negative formal
charge, O would be the better choice to be negative since it � s more
electronegative.)Q: How do I draw a Lewis structure of an ion?A: If it � s a
negative ion, add the negative charge to the valence. If it � s a positive ion,
subtract the positive charge from the valance. In either case put [ ] around the
entire structure, and write the charge outside the brackets.Q: How do I find the
formal charge of an element?A: Group number � lone electrons (dots) � � of the
bonded electronsQ: How do I use formal charge to determine the central atom?A:
Draw all the possible structures, trying each one in the center. Find the formal
charge for each structure. Whichever structure has the least amount of formal
charge (often the least number of atoms that have formal charge) is the best
structure. (NOTE: All of the structures should add up to the same charge � zero
for a compound, or the charge of the ion if it � s an ion)
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####Y^ � � ] � # #U � � j � h ?#G#d � ####P � �
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# �M � d �
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% � � t ## � @ � ; � u # � A 0 � # � I �

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T$8 � T$` � ALP � � # ## � � # � � # � - ###Pj # � L$< � #
## � |
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SV � � F W � ~@98u# � }##u
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� U#;M � u'Wj # � E � P � � � D # ## � # � P # � # � S # � C ## � � _ ^[ � � ] � # # � u � � S # ## � u � M � W # � �
� ‫݌‬##r# � G# � # � G #RP � A#Pj # � +## � � } # � M � W � } #Q � M
� U � R 랋 E � _ � 3 � C #^ � C## � � [ � � ] � # # U � � � # S � ]
VW � � G # � 0 � # � � t # ; � t # � � # # � ]
9u#u[ � M# � w# � # � � t # ; � t # � r � # # � ]
9u#u> � O# � Q#R � � � # # # � G # � @# � G# � G##### � # � G# � @ # � G# � # � E # � # � # � H #_^[ � � ] � # # �
� t#;]#t# � # � ## � ]
� M#;M#t# � u
�M � � � # ## � E � PS � M � QW � �
## � ]
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� E# � 8_^ � H#[ � � ] � # #U � � j � h � 3 G #d � ####P � � L SV � � S I#3 � P � E � d � # ### � � ‫ ݌‬#CDD#r<j #
3 � hLSH# � M � � E � # ### � u � � E � # � � � � � u � E � P � M � � 0 � � � h � � H # � M � Q � K
## � U# � G#RPVP � ### �ȋG# � #####_# � M#; � u# � H# � G# � # � W # � J # � ! � }
#t� # � G#;0u# � # � # � N # � G #;p#u# � H# � Q# � zH# � A# � � # � ! ### � # � Q #;
# � � # ## � R# � zH#u# � YH � ZH � # � J # � A H# � # � r # � � # ##;q#u#W � � � # ## � F# � XH � N# � Q # � BH#
� F# � @# � # � Q # � # � Q # � z I#u# � B# � P# � Q# � W#;B#u# � J# � A# � ### � P#;B#u# � J# � A# � } �
� A# � v � # � z H#u# � YH � ZH � # � J # � A H# � # � r # � [;1u#W � � � # # # � F# � XH � N# � Q# � B H# � F# � @
# � H# � # � P # � # � z I#u# � B# � P# � Q# � W#;B#u# � J# � # � P #;#u# �
� # � J # � # � H # � N # � y H# � F## � � � � � M # � W # � B # � X H � E# � H# � # � # � M � d � ####Y^[ � � ] �
# � � � � � U � � Q � @ # V � p # � ~I# � E � u CS � _# � # � � # # ## � ‫݌‬## � W# � N
t � [^ � � ] � � � � � U � � j � h ` =G#d � ##
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�E � � s
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º#Y � #+Ѓ � #s# � ###@ � U � ; � # � d ### � � � � # Y � # + � ; � s
� E � # ### � U � � # #щU � ; � s # � E � � Ћ � � � # # # � � t � � � � M # + K
� � B# � � � # � � � # � � � � # # � | � � � 3
�x � � � � E � k � \ # � � U � � p # � ` � � � � x � � � � E # P � K
Q� �t � � � � � � E ## Dž x � � � # # ## � � | � � � B k � \ #‫݌‬C#P � M#Q � " ## � E � � � � � K # � {
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R� �## � �
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� e### � � |
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� � V � F � # # � � # j #j # � 7###+M# � � B # � � � # � � � # � � � � # # ƒ � # # � � # # # � M � Q � M � � C � � �
� E � # ### � E# � P\ � K#QP � ,### � E � # � { # � � + M # � � B # � � � # � � � # � � � � # # ¾ ####+ � U � �
� � � E � # ### � C#\ � [# � M � Q � { � � E # � # ### � � # � r � � |
� � � � z # � � \ � M # � � \ � � � j # j # � ### � E � P � M � 谲��
�E � #### � s# � ~ � V W � � � # # # � C # � E � # � M � Q � U � R � E � P V � Nj } # � 0 ## � M � Q � E # � x \ � ### �
�# �E � � � � � M � � + � � � � M � d �
####Y_^[ � M � 3 � � � # # � � ] � # # � � � � � � � � � � � � � U � � � � j � h � 3 G #d � ####P � � L � �
SI#3 � P � D$Pd � ####j #h � PH# � L$# � D$(#### � D$$#### � D$## � B � � � � D $ X#### � D$#P � L$
( � l � � � h � � H # � L $(Q � ### � � � � � � � � � � � � � U � � �
� � w #3 � k � \ Q � � # # � � # � � ] Ã � 3 � � � � \ s � j # � M � � ^ � � � h @ � H # � E � P � 9 ### � � � � � �
� � � � � � � � � � U � � Q � F # � N ## � SW � � # u# � � # � � # 9 F#w#V � #### � ^##^# � F# � � � � # ; �
w#+ � V# � < � # u#j # �
� ## � N# � � # � # � � V # � # � � � # � # � � � t # � M # � # � # � F #_[Y] � ## � � � � � � � � � � � � �� A
# � � t # � � � A # u# � A##### � � � � � � � � � � U � � j � h ` #G#d � ####PQV � � S I#3 � P � E � d � # ##
# � u#Q � e � e � � � # # � E � # ### � ### � F# � @E# � F# � @# � F# � # � F # � @ # � F ##### � E � � � � � Ƌ M
�d �
####Y^ � � ] � # # � � � � � � � U � � j � h 0 ,G#d � ####P � � # SVW � � S I#3 � P � E � d � # ### � e � u #Q
� e � e � � f � # # � E � # ### �
### � F# � @E# � F# � @# � F# � # � F # � @ # � F##### � E � # � E
P� � � ,
## � E � � � � � Ƌ M � d �
####Y_^[ � � ] � # # � u # � ###j #j # � g### � � � � � � � � � � � � � � U � � � # � U # S � ]
VW � � B # � p# � ~ E# � Ȱ # � M
� E � u K � # � � $ # ### � ~$# � N � u
r# � F# � # � F #QP � G#Pj # � � � � ! # # � � # � # E � � t # � 6 � # � v # � ~ E#tċM
� U# � 2 � M � u � � t R � B # � # � E � � t # ; � t # � � � # # � M
� U#;M � u'Wj # � E � P � � � t # ## � # � P # � # � S # � C ## � � _ ^[ � � ] � # # � u � � # ## � u � M � W # � �
� ‫݌‬##r# � G# � # � G #RP � A#Pj # � <!## � � } # � M � W � } #Q � M
�U �R 랋
E � _ � 3 � C #^ � C## � � [ � � ] � # # U � � j � h � 3 G#d � ####P � � L SV � � S I#3 � P � E � d � # ### � � ‫ ݌‬##
I � #r<j #3 � hLSH# � M � � E � # ### � u � � E � # � ‫ � ݌‬u � � � � E � P � M ‫ ݌‬谪�
�h � � H # � M � Q � � # # # � U # � G #j #RPVP � ### �ȋG# � #####_# � M#; � u# � H# � G# � # � W # � J # � ! � }
#t� # � G#;0u# � # � # � N # � G #;p#u# � H# � Q# � zD# � A# � � # � ! ### � # � Q #;
# � � # ## � R# � zD#u# � YD � ZD � # � J # � A D# � # � r # � � # ##;q#u#W � � � N
## � F# � XD � N# � Q# � BD# � F# � @# � # � Q # � # � Q # � z E#u# � B# � P# � Q# � W#;B#u# � J# � A# � ### �
P#;B#u# � J# � A# � } �
� A# � v � # � z D#u# � YD � ZD � # � J # � A D# � # � r # � [;1u#W � � � +
## � F# � XD � N# � Q# � BD# � F# � @# � H# � # � P # � # � z E#u# � B# � P# � Q# � W#;B#u# � J# � # � P #;#u#

� # � J # � # � H # � N # � y D# � F## � � � � � M # � W # � B # � X D � E# � H# � # � # � M � d � ####Y^[ � � ] �
# � � � U � � Q � @ # V � p # � ~ E# � E � u CS � _# � # � � # # ## � ‫݌‬## � W# � N
t � [^ � � ] � � � � � U � � � � F # � # � # �
r# � # � # � � R � Q #PRj # � ### � � } # � v # � # � u � 6 � ~ E# tE
� #PQRQ � D$#P � � � ` # ## � N#Q � � # # � � # 3

F# � F# � � ] � � � � � � � �� # Q � t � # #Y � � � � � � � U � � j � h X 3G#d � ####PQV � � S I#3 � P � E � d


� #### � E � PQ � 2 7## � E � ####P � >## � � # � � � E � � � � � M � � t # � M X## � � t
� # �ȋ #j # � Ћ# � E# � R#P � � ҋ M � d �
####Y^ � � ] � # #U � � j � h � ; G#d � ####P � � L SVW � � S I#3 � P � E � d � # ### � E# � xI#t<j #3 � h`SH
# � M � � E � # ### � u � � E � # � 0 � � � � u � E � P � M � � ! 6 ##h � H# � M � Q � | � # # � ‫؍‬u# � ] � � f
## � # � yI#t# � {# � # � S # � zI#t# � � �
� E# � x# � P#; � u‫݌ � ݌‬I# � s#u# � w# � U# � B#9X#u# � x# � #9#u# � > � # � ~ # � B #9#u# � ‫݌‬I#t# � � � #
� # � x I# � � u
�ȋ# � xI#t � B# � # � J # � M � 9 Y## � � # ## �‫ ݌‬I#t# � Ɖ A# � t � � �
## � M � U# � A# � b � A # � # � # ;C#u# � � � # � ‫ ݌‬I # � p #u# � w# � > � K # �
� S# � B# � M# � I#9Y#u# � A# � # � K #9#u# � # � # � A # � S # � P # � K H � � H ; � t # � # � # � # � # � U # � E �
#8XH# � #### � J#;y## � � # ## � d$#8_H# � � # ## � #; � ui � N# � yH#u# � YHR � � � F H # � ) ### � N# � U
# � yI#ux � #8XHu# � A#8XHte � A#8XHu# � # � XHR � AH# � W### � N# � U# � FH � AH � ^H � I # � YHR � � �
� ### � x � y H#u# � YHR � � � F H # � # ### � # � U # � yI#u# � A#8XHu# � #8XHu# � AH# � J# � � � v # ;y##
� D � � � � 2 � # 8 XHu# � A# � XHR � AH# � {### � # � U # � F H � A H � ^H �
� YHR � � � � # # # � _ H � E � � � � � U � �
R �* � � � E � P � = � # # � M # � A # � � # � � v # H � A # � U
� E# � � B# �
� ‹M � d �
####Y_^[ � � ] � # # � � � � � � � � � � � � � U � � A # � # � Q # � # � z I#u# � J# � Q# � P# � U# � R#;J#
u
� B# � # � A #] � ## � Q#;
u# � # � # � A #] � ## � B# � # � A #] � ## � � � � � � � � � � � � � � � U � � # � P # � # � P # � z I#u# � J#
� Q# � P# � U# � R#;J#u� B# � H# � A#] � ## � Q#;J#u
� B# � H# � A#] � ## � # � H # � A #] � ## � � � � � � � � � � � U � � j � h p #G#d � ####P � �
SVW � � S I#3 � P � E � d � # ### � e � j L � 0 � # # � � # � E � � E � # # ## � � t # � # #### � #### � U � H# � � t
# � ##### � E � #### � H# � � t # � # #### � E � � � � � P H � @ I# � M � d �
####Y_^[ � � ] ËE � P � � # # � � # j #j # � � # # � � � � � � � � � U � � j � h � ; G #d � ####P � �
SVW � � S I#3 � P � E � d � # ### � e � j L � � # # � � # � � u � � E � # # ## � u � � E � # � � t # � E #P � M#QV �
U# � M

## � E � # � E � � � � � Ƌ M � d �
####Y_^[ � � ] � # # � U � R � # � # # � � # j #j # � � � # # � � � � � � � � � � U � � �
S � ]# � K# � � � � # + � V W � E ##### � � # s# � � # ## � � � � � # s # � # ### � # � � # v # � � � � # + � ; � w
# � E# � {# � E# � � # #ȉ} � # � � # ## � # � # ###R � � # # � K # � E � C ##
4 � #### � ### � + � #IU � U � � � # # ‫݌‬
� #####у � # � U � � v # � E � Q PQ � M � # #P � � # # � U � � # � E # ; � w n � C # � # � ‫ ݌‬4 � # ### � u � # � � v # �
M � QPQR � p � ## � � # � M # + � t 3# � � } � # � � # # # � ϋ } � � |
� � 3 � � � � # # � E � � � j # � M � �݃���h@ � H# � M � Q � � # # � K # � < � # ### � � � � # � � v # # � # � P Q
PR � # � ## � � # � C # � U �
#+ � # � � # � # � # ### � <# � � v
PQPR � � � # # � � # � M # � � v # 3 � � C # � � t
P � V � ## � � # � U � E ##C#_^ � S#[ � � ] � # # � � U � � � # S � ]
VW � � G # � 0 � # � � t # ; � t # � ? � # # � ]
9u#u[ � M# � w# � # � � t # ; � t # � " � # # � ]
9u#u> � O# � Q#R � � � � # # # � G # � @ # � G# � G##### � # � G# � @# � G # � # � E # � # � # � H #_^[ � � ] � # #
� � t #;]#t# � � � # # � ]
� M#;M#t# � u
� M � � # ## � E � P S � M � Q W � � # # # � ]
�ȋ?
� E# � 8_^ � H#[ � � ] � # #U � � S � ] #V � � C #W � ~ # � � # � # WP � � � # # # � G # � K# � V# � N# � B# � x E#u
A � # � yE#u# � d$# � K# � yE#t � # � v # � N # � A # � x E#u# � # � I # �ȋA# � xE#t � _ � N #^[] � ## � # � v #_
� v#^[] � ## � � � � � � � � � � � � U � � A # � # � Q # � # � z E#u# � J# � Q# � P# � U# � R#;J#u
� B# � # � A #] � ## � Q#;
u# � # � # � A #] � ## � B# � # � A #] � ## � � � � � � � � � � � � � � � U � � # � P # � # � P # � z E#u# � J#
� Q# � P# � U# � R#;J#u� B# � H# � A#] � ## � Q#;J#u
� B# � H# � A#] � ## � # � H # � A #] � ## � � � � � � � � � � � U � � j � h A !G#d � ####P � �
SVW � � S I#3 � P � E � d � # ### � e � j H � # � # # � � # � � u � � E � # # ## � u � � E � # � � t # � E #P � M#QV
� }# � U# � M
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## � E#P � � $ � � � Q � �
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d � #### � u#Q � e � e � � P # # � E � # ### � E# � M# � U#P � E
Q � M#RPQV � *### � E � � � � � Ƌ M � d �
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SVW � � S I#3 � P � E � d � # ### � e � u #3 F
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# � # � #3## � E
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� # � Q # � ## � # � � # � P# � � ҃ � u # # � ËF
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t#j # � � ' ##2#M � d �
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E � � F `8TH# � Fh � UH# � E � # ###S � Ή} � � � # # # � } � F ` � # #VH# � FL$VH# � P# � NL � D2`,VH# � F` �


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####Y^ � � ] � � � � � � � � � U � � j � h 0 %G#d � ####PV � � S I#3 � P � E � d � # ### � u# � E
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####Y^[ � � ] � U � � j � h V )G#d � ####PQSVW � � S I#3 � P � E � d � # ### � ]
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E � � F `8TH# � Fh � UH# � E � # ###S � Ή} � � � # # # � } � F ` � # #VH# � FL$VH# � P# � NL � D2`,VH# � F` �


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####Y^ � � ] ËP` � J# � D#` � M � d �
####Y^ � � ] � � � � � � + I � � h � � � � � � � � � � � U � � � l � X j #Q � M � � l # ##h � H# � E � P 臷#
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####Y^ � � ] � # # � � � � � � U � � j � h � # G #d � ####PQV � � S I#3 � P � E � d � # ### � � u � � # � U H #
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####Y_^ � � ] � # # � � � � � � � � � � U � � j � h � & G #d � ####PQV � � S I#3 � P � E � d � # ### � � u �
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