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Plots of Complex Reactions and Derivation of

Formulas for Each Concentration


Jermaine Angela B. Prieto, BSChE 3B
Bicol University, Legazpi City Philippines; jermaineangelabersabe.prieto@bicol-u.edu.ph

Abstract – Complex chemical reactions, such as product increases, the rate of the reaction also increases. A
irreversible reactions in parallel, autocatalytic reactions, classic example is the Belousov-Zhabotinsky reaction:
irreversible reactions in series, and first-order reversible
reactions, play significant roles in nature and industry. 2𝐵𝑟𝑂"# + 𝐶𝐻! (𝐶𝑂𝑂𝐻)! + 𝐻$ → 2𝐵𝑟 # + 𝐶𝑂! + 2𝐻! 𝑂
This paper explores the kinetics and mechanisms of these
reactions, employing Levenspiel's plots and Microsoft In irreversible reactions in series, the products of one
Excel for validation. Through detailed analysis, we reaction become the reactants for the next reaction. Each step
confirm Levenspiel's figures and reveal insights into how in the series contributes to the overall transformation of the
factors like temperature and concentrations influence initial reactants into the final products. An example is the
reaction rates and completion times. Our findings combustion of methane:
highlight the intricate nature of these reactions, providing
valuable insights for optimizing conditions in chemical 𝐶𝐻% + 2𝑂! → 𝐶𝑂! = 2𝐻! 𝑂
processes, particularly in industries reliant on efficient 𝐶𝑂! + 𝐶 → 2𝐶𝑂
and controlled reactions. 1
Index Terms: autocatalytic reactions, concentration, first- 𝐶𝑂 + 𝑂! → 𝐶𝑂!
2
order, parallel
First-order reversible reactions involve a forward and
INTRODUCTION reverse reaction occurring simultaneously, with the rate of
Chemical reactions in nature and industry can exhibit a reaction depending on the concentration of the reactants. A
variety of complexities beyond simple one-step processes. common example is the decomposition of nitrogen dioxide:
These complexities often arise from the interaction of
multiple reactants, intermediates, and products. In this paper, 2𝑁𝑂! ⇋ 2𝑁𝑂 + 𝑂!
we delve into the realm of complex reactions, exploring
different types such as irreversible reactions in parallel, In this paper, we will explore the kinetics and
autocatalytic reactions, irreversible reactions in series, and mechanisms of these complex reactions, considering how
first-order reversible reactions. factors such as temperature, concentration, and catalysts
The primary chemical process is occasionally influence their behavior. By studying these, we aim to gain a
accompanied by a few side reactions. Since these reactions do deeper understanding of the intricate nature of chemical
not occur in a single step, they are referred to as complex reactions and their applications in various fields.
reactions. In other words, rather than occurring in a single METHODOLOGY
step, such complicated reactions happen in a sequence of
steps, and the overall reaction rate follows the reaction's This section of the paper is divided intro three distinct parts.
stoichiometric equations. The following types of complex Each part covers the confirmation of Figures 3.7, 3.9, 3.11-
reactions occur: 3.12: Levenspiel’s plot for complex reactions. For execution
Irreversible reactions in parallel occur when multiple of the graphs, Microsoft Excel was used.
reactants independently proceed to form different products. I. Confirmation of Figure 3.7 (Concentration vs.
This means that the reaction pathways are distinct and do not time graph of Irreversible Parallel Reactions)
influence each other. An example of this type of reaction is
the decomposition of hydrogen peroxide 𝐻! 𝑂! : According to Octave Levenspiel, given the irreversible
1 parallel reaction, which is the decomposition of A by either of
𝐻! 𝑂! → 𝐻! 𝑂 + 𝑂!
2 the two paths:
𝐻! 𝑂! → 𝐻! 𝑂 + 𝑂! 𝐴→𝑅
Autocatalytic reactions involve a product that acts as a 𝐴→𝑆
catalyst for its own formation. As the concentration of the
The graph of concentration versus time is shown in values were used to generate a 2D line graph to represent the
Figure 3.7 below: changes in the concentrations of reactant as the reaction
progresses.

FIGURE I
CONCENTRATION VS. T

To validate this using the Microsoft Excel, various


derivations were needed. These derivations are all in the
Appendix. Using Microsoft Excel, constants were first set for
the reaction. For the first objective, the following were the
values for activation energy, frequency factor, gas constant,
initial concentration (𝐶&' ), temperatures 1 and 2, and the rate FIGURE III
constants (k). The values of rate constants were obtain by VALUES OF CA, CR, AND CS WITH TIME
using Arrhenius Law where the formula for k is: Assuming that the second reaction is second order,
(
𝑘 = 𝐴𝑒 #
)* another table is constructed with the same formula as the
previous table I for 𝐶& and 𝐶) and newly derived equation for
𝐶, . Given the rate equation:
𝑑𝐶&
−𝑟& = − = 𝑘+ 𝐶& + 𝑘! 𝐶&! (7)
𝑑𝑡
𝑘) 𝐶(* 𝑒 +,' -
𝐶( = (8)
𝑘) + 𝑘. 𝐶(( − 𝑘. 𝐶(/ 𝑒 +,' -
FIGURE II Equation (8) was used to calculate for the 𝐶& in the
ASSUMED VALUES FOR PARALLEL REACTION
second table. With the same four columns and time intervals,
To construct the table for the graph, concentrations of the same steps were followed as per the previous table. The
participating reactants are needed. To obtain these, all difference were just the formulas for the concentrations of 𝐶&
concentrations were derived from the rate equation: and 𝐶,. For the latter, the derived formula was:
!
"#! 𝑘! 𝐶&'
−𝑟! = − = 𝑘% 𝐶! + 𝑘& 𝐶! (1) 𝐶, = (1 − 𝑒^ − 2𝑘′𝑡) (9)
"$ 2𝑘′
𝑑𝐶&
𝑟) = − = 𝑘+ 𝐶& (2)
𝑑𝑡
𝑑𝐶&
𝑟, = = 𝑘! 𝐶& (3)
𝑑𝑡
For the table, four columns were set for the reaction time,
and concentrations of A, R, S. These show how the
concentration changes with time. The following were the
formulas used for the concentrations of each reactant:
𝐶& = 𝐶&' 𝑒 #(."$.#)0 (4)
1 −(𝑘 +𝑘 )𝑡
𝐶! = 𝑘" 𝐶#$ $ %1 − 𝑒 1 2 &' (5)
𝑘1 + 𝑘2
𝑘! 𝐶&' $
𝐶, = <1 − 𝑒 #. 0 = (6)
𝑘′
With these derived equations, the values started in row
12, with cell A12 set to 0 for initial time followed by 0.2 up FIGURE IV
until 6. The time interval was 0.2 unit time. For cell B12, the VALUES OF CA, CR, AND CS WITH TIME FOR 2ND ORDER
used in MS Excel was = $𝐵$5 ∗ 𝐸𝑋𝑃(−($𝐸$4) ∗ 𝐴12). For
cell C12, the formula was = $𝐸$2 ∗ $𝐵$5 ∗ (1/$𝐸$4 ∗ (1 − After obtaining the values using equations (8) and (9), the
𝐸𝑋𝑃(−($𝐸$4) ∗ 𝐴12))). Lastly, for cell D12 (𝐶) ), = values of 𝐶) used was the same 𝐶) from the previous derived
(($𝐸$3 ∗ $𝐵$5)/$𝐸$4) ∗ (1 − 𝐸𝑋𝑃(−($𝐸$4) ∗ 𝐴12)). formula for 𝐶) . In both tables, it is assumed that 𝐶)' = 𝐶,' .
After obtaining values in A-D12, they were all dragged down The table in Figure IV is then made into a 2D line graph
until time of 6 unit time (reaction until 6 unit time). These
showing concentrations of each with time as the reaction creating a table of 4 columns with the following labels
progresses. respectively: time, −𝑟& , 𝐶& /𝐶&' , and 𝐶& . For this table, the
II. Confirmation of Figure 3.9 for Autocatalytic time increment was set to 5 unit time. Hence, the time was
Reactions from 0-300 in 5 unit time intervals. For −𝑟& , and 𝐶& the
Figure 3.9 as shown by Levenspiel in the book depicts following formulas were used:
the relationship of time with conversion and the rate- −𝑟& = 𝑘𝐶& [(𝐶&' + 𝐶)' ) − 𝐶& ] (11)
conversion curve for autocatalytic reactions. Given the 𝐶𝐴0 𝐶0
reaction 𝐴 + 𝑅 → 𝑅 + 𝑅, the graphs were: 𝐶& = (𝐶 +𝐶 )𝑘𝑡 (12)
𝑒 𝐴0 𝑅0 (𝐶0 − 𝐶𝐴0 ) + 𝐶𝐴0

FIGURE V
CONVERSION VS. TIME AND RATE VS. CONCENTRATION GRAPH FOR
AUTOCATALYTIC REACTIONS

To confirm this graph, values for activation energy,


frequency factor, gas constant, initial concentrations for A FIGURE VIII
TABLE OF VALUES FOR RATE-CONCENTRATION GRAPH
and R, temperature, M, 𝐶2 , and rate constant 𝑘+ were set. For
the autocatalytic reaction, the following were used: A concentration vs. time graph was also generated from
the table in Figure VIII.
III. Confirmation of Figures 3.11 and 3.12 for
Chain of Successive First-Order Reactions
0" 0# )# )$ )% )&
Given the reactions 𝐴 → 𝑅 → 𝑆 and 𝐴 → 𝑅 → 𝑆 → 𝑇 → 𝑈 ,
the following were the generated graphs by Levenspiel:
FIGURE VI
CONSTANTS FOR AUTOCATALYTIC REACTION

A table of two columns was created in cells A13-A24 and


B13-B24 dedicated for time and conversion (𝑋& ) wherein the
time per conversion was identified using the derived equation:
𝑀 + 𝑋!
ln
𝑀(1 − 𝑋! )
t= (10)
(𝐶'( + 𝐶)( )𝑘
The formula for MS Excel is therefore = 𝐿𝑁(($𝐵$8 +
𝐵14)/($𝐵$8 ∗ (1 − 𝐵14)))/(($𝐵$6 + $𝐵$5) ∗ $𝐵$10).
Making this into a scatter-plot graph where the x-axis is the FIGURE IX
time and the y axis is the conversion, the first graph of figure CONCENTRATION VS TIME CURVES FOR FIRST REACTION

3.9 is then confirmed.

FIGURE VII
TABLE OF VALUES FOR CONVERSION VS. TIME GRAPH

To confirm and validate the second graph of parabola, FIGURE X


rate and concentration must be identified. This was done by CONCENTRATION VS TIME CURVES FOR SECOND REACTION
The curves above are confirmed and validated by using Another line graph showing the concentrations of each
these methods: reactant per time is then generated after creating the table of
First, constants were set, but this time, there were four values. For the second table (shown in Figure XV), the same
different temperatures and four different rate constants from table is copied but with added 2 more columns to be labeled
T1-T4 and k1-k4. The following were the constants set to 𝐶* 𝑎𝑛𝑑 𝐶3 . The derived formulas for 𝐶& and 𝐶) are the same
create the table of values for the curves: with Equations (13) and (14). The rest of the formulas are as
follows:
𝑘! 𝑘+ 𝐶&' (𝑒 #."0 − 𝑒 #.(0 )
𝐶, = SNS T
𝑘! − 𝑘+ 𝑘" − 𝑘+
(𝑒 #.#0 − 𝑒 #.(0 )
FIGURE XI −S TOT (16)
CONSTANTS FOR CHAIN OF SUCCESSIVE FIRST ORDER REACTIONS 𝑘" − 𝑘!
𝑘" 𝑘! 𝑘+ 𝐶&' 1 (𝑒 #."0 − 𝑒 #.)0 )
𝐶* = UV NS T
𝑘! − 𝑘+ 𝑘" − 𝑘+ 𝑘% − 𝑘+
FIGURE XII (𝑒 #.(0 − 𝑒 #.)0 )
TEMPERATURE AND RATE CONSTANTS FOR IRREVERSIBLE SERIES REACTION −S TOW
𝑘% − 𝑘"
1 (𝑒 #.#0 − 𝑒 #.)0 )
−V NS T
𝑘" − 𝑘! 𝑘% − 𝑘!
FIGURE XIII (𝑒 #.(0 − 𝑒 #.)0 )
TEMPERATURE AND RATE CONSTANTS FOR CHAIN OF SUCCESSIVE FIRST- −S TOWX (17)
ORDER REACTION 𝑘% − 𝑘"
Two more table of values shall be created, one for Figure
3.11, and the other is for Figure 3.12. For the first table, four
columns were created each for time, concentration of A,
concentration of R, and concentration of S. The derived
formulas for 𝐶& , 𝐶) , and 𝐶, were:
𝐶& = 𝐶&' 𝑒 #."0 (13)
𝑒 #."0 𝑒 #.#0
𝐶) = 𝑘+ 𝐶&' N + O (14)
𝑘! − 𝑘+ 𝑘+ − 𝑘!
𝑘! 𝑒 #."0 𝑘+ 𝑒 #.#0
𝐶, = 𝐶&' N1 + + O (15)
𝑘+ − 𝑘! 𝑘! − 𝑘+
The formulas in cells B13, C13, and D13 were = $𝐵$5 ∗
𝐸𝑋𝑃(−($𝐷$8 ∗ 𝐴13)), = $𝐷$8 ∗ $𝐵$5(((𝐸𝑋𝑃(−($𝐷$8 ∗
𝐴13)))/($𝐷$9 − $𝐷$8)) + ((𝐸𝑋𝑃(−($𝐷$9 ∗ 𝐴13)))/ FIGURE XV
($𝐷$8 − $𝐷$9))), and = $𝐵$5 ∗ (1 + (($𝐷$9 ∗ TABLE OF VALUES FOR CHAIN OF FIRST ORDER REACTION
𝐸𝑋𝑃(−($𝐷$8 ∗ 𝐴13)))/($𝐷$8 − $𝐷$9)) + (($𝐷$8 ∗
𝐸𝑋𝑃(−($𝐷$9 ∗ 𝐴13)))/($𝐷$9 − $𝐷$8))), respectively. RESULTS AND DISCUSSION
This section of the paper explains the graphs generated
and confirms each of the Levenspiel’s plots for different
complex reactions. This shall contain interpretations of each
graph generated from all the table of values.
I. Confirmation of Figure 3.7 (Concentration vs.
time graph of Irreversible Parallel Reactions)

FIGURE XIV FIGURE XVI


TABLE OF VALUES FOR IRREVERSIBLE SERIES REACTION
CONCENTRATION VS TIME GRAPH OF IRREVERSIBLE PARALLEL REACTIONS
IN FIRST ORDER
Figure XVI confirms the Levenspiel’s plot Figure 3.7. increases with respect to time. It provides a visual
This graph indicates that as the reaction proceeds, the representation of how the concentration of reactants changes
concentration of A decreases and concentration of R and S over time and how this affects the rate of product formation.
increases as k1>k2 the concentration of B increases more When the initial concentration of A is increased, the graph
rapidly than concentration of S. becomes steeper. Therefore, it then takes less time for the
To know how other parameters such as the constants conversion to reach 1. When 𝐶)' > 𝐶&' , the graph shifts to a
affect the reaction, each constant was manipulated starting shape that’s almost like half a parabola, a wide inverted “U”.
from the activation energies. Increasing the activation energy When otherwise, the graph imitates the letter “S”.
by 1000 shifted the graph, making the lines closer to each
other. Decreasing the activation energy by also a thousand
made the lines a bit distant from one another. This means that
the higher the activation energy is, the faster is the reaction,
the faster reactant A is consumed, the more its concentration
is decreased.
Increasing the initial concentration from 15 to 50
increased the rate of the reaction. This speeds up the reaction
and this is because increasing the concentration of the FIGURE XVIII
reactants will increase the frequency of collisions between the RATE VS CONCENTRATION PLOT FOR AUTOCATALYTIC REACTIONS

two reactants. When collisions occur, they do not always This also confirms Figure 3.9 of Levenspiel’s plot for rate
result in a reaction (atoms misaligned or insufficient energy, vs concentration of autocatalytic reactions. Exactly a
etc.). Higher concentrations mean more collisions and more parabola, the graphs explains that the reaction In an
opportunities for reaction. autocatalytic reaction where A is converted into product R,
Decreasing k1 and making k2>k1 results to a more rapid and R acts as a catalyst for the conversion, the plot might start
increase of the concentration of S than R. If k1 > k2 the with a low rate at low concentrations of R, then sharply
reaction A ⎯→ R will be the major reaction and A ⎯→ S will increase as R concentration rises (indicating autocatalysis),
be the side or parallel reaction. reach a peak rate, and then start to level off or decrease
slightly at very high concentrations of R. As concentration of
autocatalyst inceases, the rate of reaction also increases.

FIGURE XVII
CONCENTRATION VS TIME GRAPH OF IRREVERSIBLE PARALLEL REACTIONS
IN 2ND ORDER FIGURE XIX
RATE VS CONCENTRATION PLOT FOR AUTOCATALYTIC REACTIONS
This is the graph of the irreversible parallel reaction if the The figure above shows the concentration vs. time plot of
second reaction is in second order. It shows the more rapid autocatalytic reactions wherein the reaction starts slowly at
increase of the concentration of S than R. first, and then speeds up before slowing down again and
II. Confirmation of Figure 3.9 for Autocatalytic eventually stopping.
Reactions III. Confirmation of Figures 3.11 and 3.12 for
For autocatalytic reactions, the conversion-time graph Chain of Successive First-Order Reactions
generated from the table of values was: The table of values for series reaction resulted to the
graph below, which confirms Levenspiel’s plot in Figure
3.11.

FIGURE XVII
CONVERSION VS. TIME PLOT FOR AUTOCATALYTIC REACTIONS
This confirms Figure 3.9 of Levenspiel for 𝑋& 𝑣𝑠 𝑡 of FIGURE XX
autocatalytic reactions. The graph shows that the conversion CONCENTRATION VS. TIME PLOT FOR SERIES REACTION
Figure XX validates Figure 3.11 of Levenspiel and it can off. In series reactions, reactants transformed into
be seen that A decreases steadily over time, R first goes up intermediates and then products, with different reactions
and then down, and S starts from zero and gradually increases influencing each other's rates. These insights are crucial for
until it reaches the same amount as the initial concentration of industries to optimize conditions and reduce waste. This study
A, showing that all of A has turned into S by the end. offers a clearer understanding of complex reactions, aiding in
Increasing the temperature also increases the rate advancements in chemical engineering and related fields.
constant (k). the faster the reaction, the lesser time it will take
for the reaction to halt. If the initial concentration of A is ACKNOWLEDGMENT
increased, the graph does not show much of a difference The researcher would like to express her deepest gratitude to
however the table of values display largest differences of the following:
concentrations therefore, it can be said that the higher the First, to the Father Almighty, for His guidance and
concentration of the reactants, the faster is the reaction rate. light that helped me finish this paper despite the tight
schedule.
Second, to Engr. Junel B. Borbo for allowing us to
have more time for our Machine Problem, for the very useful
and comprehensive learning modules, and for being very
considerate. I appreciate you so much, Sir.
To Alex, Junella, Naomi, Raiza, Ianna, and Yai, for
entertaining every question I have in mind, for keeping me
sane, and for helping me every time I needed a hand.
Lastly, to my friends and family who served as my
FIGURE XXI support system and helped me stay sane despite my busy and
CONCENTRATION VS. TIME PLOT FOR CONSECUTIVE FIRST ORDER REACTION
The figure above validates Figure 3.12 showing the same jampacked schedule. I am extremely thankful for having these
reaction mechanism wherein the concentration of A decreases people.
exponentially as 𝐶) , 𝐶, , 𝑎𝑛𝑑 𝐶* increases with 𝐶, being the REFERENCES
fastest to increase, and 𝐶) being the fastest to decompose or
reach 0. 𝐶3 then increases as it eventually reach the initial [1] Chem, & Chem. (2024). M13Q2: Reaction Rates: Identifying Rates on
Concentration vs Time Plots; Rates and Reaction Stoichiometry;
concentration of A. Defining Average, Instantaneous, and Initial Rates. Unizin.org;
Pressbooks.
CONCLUSION https://wisc.pb.unizin.org/chem103and104/chapter/reaction-rates-
identifying-rates-on-concentration-vs-time-plots-rates-and-reaction-
This paper delves into complex chemical reactions like stoichiometry-defining-average-intantaneous-and-initial-rates-m13q2/
irreversible reactions in parallel, autocatalytic reactions, [2] 9.4: More Complex Reactions. (2015, December 26). Chemistry
irreversible reactions in series, and first-order reversible LibreTexts.
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Ch
reactions. After all executions in MS Excel, all graphs were emistry_Textbook_Maps/Map%3A_Physical_Chemistry_for_the_Bio
confirmed and validated. Using Levenspiel's plots and sciences_(Chang)/09%3A_Chemical_Kinetics/9.04%3A_More_Comp
Microsoft Excel, it was seen how these reactions behave with lex_Reactions
different conditions. Results showed that changing factors [3] Design for Parallel Reactions Introduction to Multiple Reactions.
(n.d.). Retrieved April 9, 2024, from http://the-seventh-
like initial concentrations and rate constants affects reaction dimension.com/images/textlev/LEVENSPIEL%20Chemical%20reacti
rates and completion times. For example, in autocatalytic on%20engineering-ch7-ch8.pdf
reactions where a product speeds up its own formation, higher [4] Vedantu. (2023, September 26). Parallel First Order Reaction Kinetics
initial product concentrations led to faster reactions. In for JEE. VEDANTU; Vedantu. https://www.vedantu.com/jee-
main/chemistry-parallel-first-order-reaction-kinetics
irreversible reactions in series, altering temperature affected
how quickly reactants turned into products, showing the
intricate nature of these processes. AUTHOR INFORMATION
The findings also revealed interesting patterns. In
irreversible parallel reactions, increasing initial reactant
concentrations or adjusting rate constants changed how Jermaine Angela B. Prieto, 3rd year Student, Department of
quickly products formed. Autocatalytic reactions showed a Chemical Engineering, Bicol University.
rapid increase in product formation with increasing
autocatalyst concentrations, reaching a peak before leveling
APPENDIX

Derivations of the formulas used for analysis:: 0


$
^ 𝑒 #. 0 𝑑𝑡
For Irreversible Reactions in Parallel: '
1 $ $
`𝑒 #. 0 − 𝑒 #. (') a
To get the 𝐶& : −𝑘 5
." 1 $
𝐴→𝑅 5
<𝑒 #. 0 − 1=
.#
−𝑘
𝐴→𝑆 1 $
<1 − 𝑒 #. 0 =
𝑑𝐶& 𝑘5
−𝑟& = − = 𝑘+ 𝐶& + 𝑘! 𝐶& = (𝑘+ + 𝑘! )𝐶& 1 $
𝑑𝑡 𝐶, = 𝑘! 𝐶&' b 5 <1 − 𝑒 #. 0 =c
4!
𝑑𝐶& 0 𝑘
^ = −(𝑘+ + 𝑘! ) ^ 𝑑𝑡 𝑘& 𝐶!(
4!* 𝐶&
$
' 𝐶4 = 81 − 𝑒 50 $ 9
𝐶& 𝑘′
𝑙𝑛 = −(𝑘+ + 𝑘! )𝑡
𝐶&'
if reaction is second order:
𝐶& = 𝐶&' 𝑒 #(."$.# )0
For 𝐶& :
To get the 𝐶) :
𝑟) = 𝑘+ 𝐶& = 𝑘+ 𝐶&' 𝑒 #(."$.#)0 𝑑𝐶&
𝑑𝐶) −𝑟& = − = 𝑘+ 𝐶& + 𝑘! 𝐶&!
= 𝑘+ 𝐶&' 𝑒 #(."$.#)0 𝑑𝑡
𝑑𝑡 𝑑𝐶*
4+ 0 − = 𝐶* (𝑘+ + 𝑘, 𝐶* )
𝑑𝑡
^ 𝑑𝐶) = ^ 𝑘+ 𝐶&' 𝑒 #(."$.#)0 𝑑𝑡 -'
𝑑𝐶*
4+* ' 3 − = 3 𝑑𝑡
0 -'( 𝐶* (𝑘+ + 𝑘, 𝐶* )
𝐶) − 𝐶)' = 𝑘+ 𝐶&' ^ 𝑒 #(."$.#)0 𝑑𝑡 1 𝐴 𝐵
= +
' 𝐶* (𝑘+ + 𝑘, 𝐶* ) 𝐶* 𝑘+ + 𝑘, + 𝐶*
Integrating:
0
By Heaviside Method:
^ 𝑒 #(."$.#)0 𝑑𝑡
'
1 0 1 1
− `𝑒 #(."$.# )0 a' 𝐴=b c =
𝑘+ + 𝑘! 𝐶& 4!6' 𝑘+
1 1 𝑘!
− `𝑒 #(."$.#)0 − 𝑒 #(."$.#)(') a 𝐵=b c =−
𝑘+ + 𝑘! 𝑘+ + 𝑘! 𝐶& 4!6# .! 𝑘+
1 .#
− <𝑒 #(."$.# )0 − 1= 1 0.
1 0.
−𝑘. -
𝑘+ + 𝑘! ,- 𝑑𝐶( + - 𝑑𝐶( / = − - 𝑑𝑡
1
<1 − 𝑒 #(."$.# )0 =
𝑘) 0.( 𝐶( 0.( (𝑘) + 𝑘. 𝐶( ) /
𝑘+ + 𝑘!
1 ( ) 1 𝐶( 𝑘. 𝑘) + 𝑘. 𝐶(
𝐶) = 𝑘+ 𝐶&' b <1 − 𝑒− 𝑘1+𝑘2 𝑡 =c 1ln − ln 4 = −𝑡
𝑘1 + 𝑘2 𝑘) 𝐶(/ 𝑘. 𝑘) + 𝑘. 𝐶(/

To get the 𝐶, : 0 (, 5, 0 )
123 . ' / .( 7
𝑑𝐶& 𝑒 0.( (,' 5,/ 0. ) = 𝑒 +,' -
𝑟, = = 𝑘! 𝐶& = 𝑘! 𝐶&' 𝑒 #(."$.# )0
𝑑𝑡 𝐶! 𝑘% + 𝐶! 𝑘& 𝐶!6
𝑑𝐶, = 𝑒 5$0"
= 𝑘! 𝐶&' 𝑒 #(."$.#)0 𝐶!6 𝑘% + 𝐶! 𝐶!6 𝑘&
𝑑𝑡
𝑑𝐶, = 𝑘! 𝐶&' 𝑒 #(."$.# )0 𝑑𝑡
4. 𝐶! 𝑘% + 𝐶! 𝑘& 𝐶!* = 𝑒 5$0" 8𝐶!* 𝑘% + 𝐶! 𝐶!6 𝑘& 9
^ 𝑘! 𝐶&' ^ 𝑒 #(."$.# )0 𝑑𝑡 𝐶! 8𝑘% + 𝑘& 𝐶!* 9 = 𝑘% 𝐶!* 𝑒 50"$ + 𝑘& 𝐶! 𝐶!* 𝑒 50"$
4.*
0 𝐶! 8𝑘% + 𝑘& 𝐶!* 9 = 𝑘% 𝐶!* 𝑒 50"$ + 𝐶! 8𝑘& 𝐶!* 𝑒 50"$ 9
𝐶, − 𝐶,' = 𝑘! 𝐶&' ^ 𝑒 #(."$.#)0 𝑑𝑡 𝐶! 8𝑘% + 𝑘& 𝐶!* 9 − 𝐶! 8𝑘& 𝐶!* 𝑒 50"$ 9 = 𝑘% 𝐶!* 𝑒 50"$
'
0 𝐶! 8𝑘% + 𝑘& 𝐶!* − 𝑘& 𝐶!* 𝑒 50"$ 9 = 𝑘% 𝐶!* 𝑒 50"$
#(." $.#)0
𝐶, = 𝑘! 𝐶&' ^ 𝑒 𝑑𝑡
'
𝑘) 𝐶(* 𝑒 +,' - 𝑀 + 𝑋(
𝐶( = ln = 𝑒 0.( (:5)),-
𝑘) + 𝑘. 𝐶(( − 𝑘. 𝐶(/ 𝑒 +,' - 𝑀 (1 − 𝑋( )
𝑀 + 𝑋( = 𝑀(1 − 𝑋( )𝑒 00( (:5)),-
For 𝐶) : 𝑀 + 𝑋( = 𝑀𝑒 00( (:5)),- − 𝑀𝑋( 𝑒 ;0( (:5)),-
𝑋( = M𝑒 0.( (:5)),- − MX< 𝑒 0.( (:5)),-
𝑟) = 𝑘+ 𝐶& = 𝑘+ 𝐶&' 𝑒 #(."$.#)0
𝑑𝐶)
= 𝑘+ 𝐶&' 𝑒 #(."$.#)0 𝑋( + 𝑀𝑋( 𝑒 0.( ( 5)),- = 𝑀𝑒 0.( (:5)),- − 𝑀
𝑑𝑡
4+ 0
𝑋( :1 + 𝑀𝑒 0.( (𝑀 + 1)𝑘𝑡 = 𝑀𝑒 0.( (:5)),- − 𝑀
^ 𝑑𝐶) = ^ 𝑘+ 𝐶&' 𝑒 #(."$.#)0 𝑑𝑡
4+* '
0
𝐶) − 𝐶)' = 𝑘+ 𝐶&' ^ 𝑒 #(."$.#)0 𝑑𝑡
' 𝑀𝑒 0.( (:5)),- − 𝑀
Integrating: 𝑋( =
0 1 + 𝑀𝑒 0.( (:5)),=
^ 𝑒 #(."$.#)0 𝑑𝑡
1
' 𝑀 + 𝑋(
0 ln
− `𝑒 #(."$.# )0 a' 𝑀(1 − 𝑋( )
𝑘+ + 𝑘! 𝑡=
1 (𝐶</ + 𝐶>/ )𝑘
− `𝑒 #(."$.#)0 − 𝑒 #(."$.#)(') a
𝑘+ + 𝑘!
1 Formula for 𝐶* (first order):
− <𝑒 #(."$.# )0 − 1= 𝐴+𝑅 →𝑅+𝑅
𝑘+ + 𝑘! 𝑑𝐶&
1 −𝑟& = − = 𝑘𝐶& 𝐶)
<1 − 𝑒 #(."$.# )0 = 𝑑𝑡
𝑘+ + 𝑘! 𝐶' = 𝐶& + 𝐶) = 𝐶&' + 𝐶)' = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
1 ( ) 𝑑𝐶&
𝐶) = 𝑘+ 𝐶&' b <1 − 𝑒− 𝑘1+𝑘2 𝑡 =c −𝑟& = − = 𝑘𝐶& (𝐶' − 𝐶& )
𝑘1 + 𝑘2 𝑑𝑡
For 𝐶, : 𝑑𝐶& 1 𝑑𝐶& 𝑑𝐶&
− =− n + o = 𝑘𝑑𝑡
𝑟7 =
84.
= 𝑘! 𝐶&! 𝐶& (𝐶' − 𝐶& ) 𝐶A 𝐶& 𝐶' − 𝐶&
80
4+*
𝑀=4 Integrating, this gives:
!*
𝐶)
!
= 𝑘! `𝐶&* 𝑒 #(."$.#)0 a 𝐶&' (𝐶' − 𝐶& ) 𝐶)'
ln = ln = 𝐶' 𝑘𝑡 = (𝐶&' + 𝐶)' )𝑘𝑡
(." $.# )0 𝐶& (𝐶' − 𝐶&' ) 𝐶&
= 𝑘! e𝐶&!* f𝑒 ! gh 𝐶&'
= 𝑘! 𝐶&* <𝑒 ! #!(." $.# )0
= Isolating 𝐶& ,
840 #!(." $.# )0
𝐶&' (𝐶' − 𝐶& )
= 𝑘! 𝐶&* <𝑒 !
= ln = (𝐶&' + 𝐶)' )𝑘𝑡
80 𝐶& (𝐶' − 𝐶&' )
𝑑 7
!
= 𝑘! 𝐶9' <𝑒 #!(."$.# )0 =𝑑𝑡 ( (( *( )
%&' BC C B ,
:0
∫:1 𝑑𝐶; = 𝑘! 𝐶&!* ∫ 𝑒 #!(."$.#)< 𝑑𝑡 𝑒 (B ((C *(BC ) = 𝑒 ((BC -(DC)./
: *
'
𝐶= − 𝐶=' = 𝑘! 𝐶9' = ∫ 𝑒 #!(."$.# )0 𝑑𝑡 𝐶&' (𝐶' − 𝐶& )
0 = 𝑒>𝐶𝐴0 +𝐶𝑅0 ?𝑘𝑡
= ∫' e #!(." $.# )0
𝑑𝑡 𝐶& (𝐶' − 𝐶&' )
𝐶&' 𝐶' − 𝐶&' 𝐶&
= ∫'
0
𝑒 #!>. $ 0?
𝑑𝑡 = 𝑒>𝐶𝐴0 +𝐶𝑅0 ?𝑘𝑡
𝐶& 𝐶' − 𝐶& 𝐶&'
+ 0
#!. $ 0
#!. $
𝑒 h
'
𝐶&' 𝐶' − 𝐶&' 𝐶& = 𝑒 (4!*$4+* ).0 (𝐶& 𝐶' − 𝐶& 𝐶&' )
1
+ $ $ (') 𝐶&' 𝐶' = 𝑒 (4!*$4+*).0 (𝐶& 𝐶' − 𝐶& 𝐶&' ) + 𝐶&' 𝐶&
− `𝑒 #!. 0 − 𝑒 #!. a
!. $ 𝐶&' 𝐶' = 𝐶& 𝐶' 𝑒 (4!*$4+*).0 − 𝐶& 𝐶&' 𝑒 (4!*$4+* ).0 + 𝐶&' 𝐶&
+ #!. $ 0 >𝐶𝐴0 +𝐶𝑅0 ?𝑘𝑡
#!. $
`𝑒 − 1a 𝐶&' 𝐶' = 𝐶& f𝐶0 𝑒 − 𝐶𝐴0 𝑒>𝐶𝐴0+𝐶𝑅0?𝑘𝑡 + 𝐶𝐴0 g
1 $
𝐶&' 𝐶'
`1 − 𝑒 #!. 0 a 𝐶& =
2𝑘 5 >𝐶𝐴0 +𝐶𝑅0 ?𝑘𝑡
𝑘. 𝐶(/ ′
−2𝑘 𝑡
𝐶0 𝑒 − 𝐶𝐴0 𝑒>𝐶𝐴0+𝐶𝑅0?𝑘𝑡 + 𝐶𝐴0
𝐶8 = 9
(1 − 𝑒 )
2𝑘
For Autocatalytic Reactions: 𝐶!( 𝐶(
𝐶! =
𝑒 (#!*8#+*)0$ (𝐶( − 𝐶!( ) + 𝐶!(
Formula for 𝑋* :
For Irreversible Reactions in Series: 1
`𝑒 (.##." )0 − 1a
0" 0#
𝑘! − 𝑘+
𝐴→𝑅→𝑆 𝑘+ 𝐶&*
𝐶) (𝑒 .#0 ) = <𝑒 (.##." )0 − 1=
Rate Equations: 𝑘! − 𝑘+
−𝑟& = 𝑘+ 𝐶& 𝑘+ 𝐶&*
𝑟) = 𝑘! 𝐶& − 𝑘! 𝐶) 𝐶) = (𝑒 #.#0 )<𝑒 (.##." )0 − 1=
𝑘! − 𝑘+
𝐶, = 𝐶&* − 𝐶& − 𝐶) 𝑘+ C9'
Formula for 𝐶* : 𝐶) = (𝑒 #.#0 )(𝑒 #."0 )(𝑒 .#0 ) − 𝑒 #.#
𝑘! − 𝑘+
𝑑𝐶& 𝑘+ 𝐶&'
−𝑟& = = 𝑘+ 𝐶& 𝐶) = (𝑒 #."0 − 𝑒 #.#0 )
𝑑𝑡 𝑘! − 𝑘+
𝑑𝐶& 𝑒 #."0 𝑒 #.#0
= −𝑘+ 𝐶& = 𝑘+ 𝐶&* N − O
𝑑𝑡 𝑘! − 𝑘+ 𝑘! − 𝑘+
4! 0
𝑑𝐶&
^ = ^ − 𝑘+ 𝑑𝑡 𝑒 #."0 𝑒 #.#0
4* 𝐶& ' 𝐶) = 𝑘+ 𝐶&* N + O
𝑘! − 𝑘+ 𝑘+ − 𝑘!
ln 𝐶𝐴 𝐶&* = 𝐶& + 𝐶) + 𝐶,
= −𝑘𝑡 𝐶, = 𝐶&* − 𝐶& − 𝐶)
𝐶&A
𝐶& = 𝐶&* 𝑒 #."0 𝑒 #."0 𝑒 #.#0
= 𝑐&* − 𝑐&* 𝑒 #."0 − 𝑘+ 𝑐&* N + O
𝑘! − 𝑘+ 𝑘+ − 𝑘!
𝑘+ 𝑐&*
Formula for 𝐶2 : = 𝑐4 − 𝐶&* 𝑒 #."0 − (𝑒 #."0 − 𝑒 #.#0 )
𝑘! − 𝑘+
𝐶&*
By Linear Differential Equation of Order One: = [(𝑘! − 𝑘+ ) − 𝑒 #."0 (𝑘! − 𝑘+ )−𝑘+ (𝑒 #."0 − 𝑒 #.#0 )]
𝑑𝑦 𝑘! − 𝑘+
+ 𝑃(𝑥)𝑦 = 𝑄(𝑥)
𝑑𝑥
𝑟) = 𝑘+ 𝐶& − 𝑘! 𝐶)
𝑑𝐶)
= 𝑘+ 𝐶& − 𝑘! 𝐶)
𝑑𝑡
𝑑𝐶) 𝑐&*
+ 𝑘! 𝐶) = 𝑘+ 𝐶& 𝐶7 = [(𝑘! − 𝑘+ ) − 𝑘! 𝑒 #."0 + 𝑘+ 𝑒 #.#0 ]
𝑑𝑡 𝑘! − 𝑘+
𝑃(𝑥) = 𝑘!
𝑘! 𝑒 #."0 𝑘+ 𝑒 #.#0
𝐼 ⋅ 𝐹. = 𝑒 ∫ K(L)8L = 𝑒 ∫ .#80 = 𝑒 .#0 𝐶7 = 𝐶&* N1 − + O
𝑘! − 𝑘+ 𝑘! − 𝑘+
𝑦 (M⋅O) = ^ 𝑄(𝑥)(𝐼 ⋅ 𝐹 ⋅)𝑑𝑡 + 𝐶
𝑘! 𝑒 #."0 𝑘+ 𝑒 #.#0
C= = C9' N1 + + O
𝐶. (𝑒 .#0 ) = ^ 𝑘+ 𝐶& (𝑒 .#0 )𝑑𝑡 + 𝐶 𝑘+ − 𝑘! 𝑘! − 𝑘0
0
𝐶. (𝑒 .#0 ) = ^ 𝑘+ 𝐶& (𝑒 .#0 )𝑑𝑡
' Chain of successive first-order reactions:
0
= ^ 𝑘+ 𝐶&* 𝑒 #."0 (𝑒 .#0 )𝑑𝑡 )# )$
𝐴→𝑅 →𝑆→𝑇→𝑈
)% )&

'
0
𝐶*( = 𝐶* + 𝐶2 + 𝐶2 + 𝐶3 + 𝐶4
= 𝑘+ 𝐶&* ^ 𝑒 #."0 (𝑒 .#0 )𝑑𝑡 𝐶4 = 𝐶*( − 𝐶* − 𝐶2 − 𝐶5 − 𝐶3
'
0 Since we have 𝐶* &𝐶2
= 𝑘+ 𝐶&' ^ 𝑒 (.##." )0 𝑑𝑡
' 𝑑𝑦
+ 𝑃(𝑥)𝑦 = 𝑄(𝑥)
𝑑𝑥
𝑑𝐶6
Integrating: 𝑟6 = = 𝑘, 𝐶2 − 𝑘7 𝐶6
𝑑𝑡
1 0 𝑑𝐶6
`𝑒 (.##.")0 a' + 𝑘7 𝐶6 = 𝑘, 𝐶2
𝑘! − 𝑘+ 𝑑𝑡
9(;)=;
1 I ⋅ 𝐹 ⋅= 𝑒 ∫ = 𝑒 ∫ )%=> = 𝑒 )%>
`𝑒 (.##.")0 − 𝑒 (.##.")(')] a
𝑘! − 𝑘+ 𝑦 ?⋅A⋅ = 3 𝑄(𝑥)(𝐼 ⋅ 𝐹 ⋅)𝑑𝑡 + 𝐶

𝐶5 (𝑒 )%> ) = 3 𝑘, 𝐶2 (𝑒 )%> )𝑑𝑡 + 𝐶


>
𝐶6 (𝑒 )%> ) = 3 𝑘, 𝐶2 (𝑒 )%> )𝑑𝑡
B
when: 𝐶2 = 𝑘+ 𝐶*( A)
C )*#+
+)
C )*$+
B 𝑘+ 𝑘, 𝐶*E > () D) )>
$ D)# # D)$
𝐶5 (𝑒 )%> ) = 3 J𝑒 % # − 𝑒 ()%D)$)> K𝑑𝑡
> 𝑘, − 𝑘+ B
𝑒 D)#> 𝑒 D)$> 𝑘+ 𝑘, 𝐶*E
𝐶5 (𝑒 )%> ) = 3 𝑘, C𝑘+ 𝐶*( D E+D EF [𝑒 )%> ]𝑡 > >
𝑘, − 𝑘+ 𝑘+ − 𝑘, 𝐶𝑠(𝑒 )%> ) = MJ𝑒 ()%D)# )> KB − J𝑒 ()%D)$)> KB N
B
>
𝑘, − 𝑘+
𝑒 D)#> 𝑒 D)$> 𝑘+ 𝑘, 𝐶*E () D) )>
𝐶5 (𝑒 )%> ) = 3 𝑘+ 𝑘, C𝑐*( D E+D EF (𝑒 )%> )𝑑𝑡 = OJ𝑒 % # − 𝑒 ()%D)# )> K − J𝑒 (;%D)$)> − 𝑒 ()%D)$ )> KP
B 𝑘, − 𝑘+ 𝑘+ − 𝑘, 𝑘, − 𝑘+
>
(𝑒 )%> )(𝑒 D)#> ) (𝑒 )%> )(𝑒 D)$> )
𝐶5 (𝑒 )%> ) = 𝑘+ 𝑘, 𝐶*E 3 C + F 𝑑𝑡
B 𝑘, − 𝑘+ 𝑘+ − 𝑘,
𝑘+ 𝑘, 𝐶*E
= OJ𝑒 ()%D)#)> − 1K − J𝑒 ()%D)$ )> − 1KP 1 𝑒 50"$ − 𝑒 50)$
𝑘, 𝑘+ ⎧ ⎡ A B −⎤⎫
𝑘+ 𝑘, 𝐶*E ) > ⎪ 1 ⎢𝑘; − 𝑘% 𝑘< − 𝑘% ⎥⎪
𝐶5 = (𝑒 % )OJ𝑒 ()%D)#)> − 1K − J𝑒 ()%D)$ )> − 1KP
𝑘, 𝑘+ ⎪𝑘; − 𝑘% ⎢ 𝑒 50($ − 𝑒 50)$ ⎥⎪
𝑘+ 𝑘, 𝐶*E ) > ⎪ ⎢ A B ⎥⎪
= (𝑒 % ) M{[(𝑒 )%> )(𝑒 D)#> ) − 1] − [(𝑒 )%> )(𝑒 D)$> ) − 1]} 𝑘% 𝑘& 𝑘; 𝐶!6 ⎣ 𝑘< − 𝑘; ⎦
𝑘, 𝑘+ 𝐶: =
𝑘& − 𝑘% ⎨ 50 $ 50 $
𝑘+ 𝑘, 𝐶*E (𝑒 D)%> )(𝑒 D)%> )(𝑒 D)#> ) − (𝑒 D)%> ) 1 𝑒 # −𝑒 )

= SC F ⎡ A B⎤
𝑘, 𝑘+ 𝑘7 − 𝑘+ ⎪ ⎢𝑘; − 𝑘& 𝑘< − 𝑘& ⎥ ⎪
(𝑒 D)%> )(𝑒 )%> )(𝑒 D)$> ) − (𝑒 D)%> ) ⎪ −⎢ ⎥ ⎪
−C F ⎪ 𝑒 50($ − 𝑒 50)$ ⎪
𝑘7 − 𝑘, ⎢ −A B ⎥
⎩ ⎣ 𝑘< − 𝑘; ⎦ ⎭
𝑘+ 𝑘, 𝐶*E 𝑒 D)#> − 𝑒 D)%> 𝑒 D)$> − 𝑒 D)%>
𝐶5 = C − F
𝑘, − 𝑘+ 𝑘7 − 𝑘+ 𝑘7 − 𝑘,
𝐶4 = 𝐶*E − 𝐶* − 𝐶2 − 𝐶5 − 𝐶3 (simplifying)
𝑟3 = 𝑘7 𝐶5 − 𝑘F 𝐶3 𝐶4
𝑑𝐶3 𝑒 D)#> 𝑒 D)$>
+ 𝑘F 𝐶3 = 𝑘7 𝐶5 (𝐿𝐸𝑂𝑂) = 𝐶*E − (𝐶*E 𝑒 D)# > ) − (𝑘+ 𝐶*E D + E)
𝑑𝑡 𝑘, − 𝑘+ 𝑘+ − 𝑘,
𝑃(𝑥) = 𝑘F
)& => 𝑘+ 𝑘, 𝐶*E 𝑒 D)#> − 𝑒 D)%> 𝑒 D)$> − 𝑒 D)%>
− C − F
𝐼. 𝐹. = 𝑒 3 𝑃9(;)=; = 𝑒 3 = = 𝑒 )& > 𝑘, − 𝑘+ 𝑘7 − 𝑘+ 𝑘7 − 𝑘,
D)# >
𝑘+ 𝑘, 𝑘7 𝐶*E 1 1 𝑒 − 𝑒 D)&>
𝑦(𝐼. 𝐹. ) = 3 𝑄(𝑥)(𝐼. 𝐹. )𝑑𝑥 + 𝑐 − S C D E
𝑘, − 𝑘+ 𝑘7 − 𝑘, 𝑘7 − 𝑘+ 𝑘F − 𝑘+
D)% > D)& >
𝐶3 (𝑒 )&> ) = 3 𝑘7 𝐶5 (𝑒 )&> )𝑑𝑡 + 𝑐 𝑒 −𝑒
−D EF
𝑘F − 𝑘7
D)$ >
)# )$ -', C )*#+ DC )*%+ C )*$+ DC )*%+
1 𝑒 − 𝑒 D)&> 𝑒 D)%> − 𝑒 D)&>
Where: 𝐶5 = X − Y −C D E−D EF\
)$ D)# )% D)# )% D)$ 𝑘7 − 𝑘, 𝑘F − 𝑘, 𝑘F − 𝑘7
𝐶*E
>
𝑘+ 𝑘, 𝑘7 𝑒 D)#> − 𝑒 D)%> 𝑒 D)$> − 𝑒 D)%> = S(𝑘, − 𝑘+
𝑘, − 𝑘+
= 3 𝑘7 D C − F 𝑑𝑡
B 𝑘, − 𝑘+ 𝑘7 − 𝑘+ 𝑘7 − 𝑘,
>
𝑘+ 𝑘, 𝑘7 𝐶*E 𝑒 D)# >
−𝑒 D)% >
𝑒 D)$ >
−𝑒 D)% > − D(𝑘, − 𝑘+ )𝑒 D)#>
=3 C − F (𝑒 )&> )𝑑𝑡
B 𝑘 , − 𝑘+ 𝑘 7 − 𝑘 + 𝑘7 − 𝑘, 𝑒 D)#> − 𝑒 D)%> 𝑒 D)$> − 𝑒 D)%>
𝑘+ 𝑘, 𝑘7 𝐶*E > (𝑒 )&> )(𝑒 D)#> − 𝑒 D)%> ) − 𝑘, 𝑘+ CD E−D EF
𝑘7 − 𝑘+ 𝑘7 − 𝑘F
= 3 C
𝑘, − 𝑘+ B 𝑘7 − 𝑘+ 𝑒 D)#> − 𝑒 D)&> 𝑒 D)%> − 𝑒 D)&>
(𝑒 )&> )(𝑒 D)$> − 𝑒 D)%> ) − 𝑘7 𝑘, 𝑘+ CD E−D EF
𝑘F − 𝑘+ 𝑘F − 𝑘7
− F 𝑑𝑡
𝑘7 − 𝑘, 1 𝑒 D)$> − 𝑒 D)&>
𝑘+ 𝑘, 𝑘7 𝐶*E > 𝑒 ()&D)#)> − 𝑒 ()&D)%)> 𝑒 ()&D)$)> − 𝑒 ()&D)%)> −[ D E
𝑘7 − 𝑘, 𝑘F − 𝑘,
= 3 C − F 𝑑𝑡
𝑘, − 𝑘+ B 𝑘7 − 𝑘+ 𝑘7 − 𝑘, 𝑒 D)%> − 𝑒 D)&>
𝑘+ 𝑘, 𝑘7 𝐶*E > 1 −D EF\
𝑘F − 𝑘7
= 3 Z𝑒 ()&D)# )> − 𝑒 ()&D)%)> [
𝑘, − 𝑘+ B 𝑘7 − 𝑘+ 𝐶*E
1 = [(𝑘, − 𝑘+ ) − (𝑘, 𝑒 D)#> − 𝑘+ 𝑒 D)#> ) − (𝑘+ 𝑒 D)#>
− Z𝑒 ()&D)$ )> − 𝑒 ()&D)%)> [ 𝑘, − 𝑘+
𝑘7 − 𝑘, − 𝑘+ 𝑒 D)$> )
𝑘+ 𝑘, 𝑘7 𝐶*E 1 𝑒 ()&D)# )> − 1 𝑒 ()&D)% )> − 1 𝑒 D)#> − 𝑒 D)%>
𝐶3 = C D E−D EF − C𝑘, 𝑘+ D E
𝑘, − 𝑘+ 𝑘7 − 𝑘F 𝑘F − 𝑘+ 𝑘F − 𝑘7 𝑘7 − 𝑘+
1 𝑒 ()&D)$)> − 1 𝑒 ()&D)% )> − 1 𝑒 D)$> − 𝑒 D)%>
−C D ED EF − 𝑘, 𝑘+ D EF
𝑘7 − 𝑘, 𝑘F − 𝑘, 𝑘F − 𝑘7 𝑘7 − 𝑘F
𝑘+ 𝑘, 𝑘7 𝐶*E D) > 1 𝑒 ()&D)#)> − 1 𝑒 ()&D)%)> − 1 𝑘7 𝑘, 𝑘+ 𝑒 D)#> − 𝑒 D)&> 𝑒 D)%> − 𝑒 D)&>
= (𝑒 & ) C D E−D EF − CD E−D EF
𝑘, − 𝑘+ 𝑘7 − 𝑘F 𝑘F − 𝑘+ 𝑘F − 𝑘7 𝑘7 − 𝑘, 𝑘F − 𝑘+ 𝑘F − 𝑘7
()& D)$ )> ()& D)% )>
1 𝑒 −1 𝑒 −1 𝑘7 𝑘, 𝑘+ 𝑘7 𝑘, 𝑘+ 𝑒 D)#> − 𝑒 D)&>
−C D ED EF − ] CD E
𝑘7 − 𝑘, 𝑘F − 𝑘, 𝑘F − 𝑘7 𝑘7 − 𝑘, 𝑘7 − 𝑘, 𝑘F − 𝑘+
𝑘+ 𝑘, 𝑘7 𝐶*E 1 (𝑒 D)&> )(𝑒 )&> )(𝑒 D)#> ) − (𝑒 D)&> ) 𝑒 D)%> − 𝑒 D)&>
= S C E −D EF^
𝑘, − 𝑘+ 𝑘7 − 𝑘, 𝑘7 − 𝑘, 𝑘F − 𝑘7
(𝑒 )&> (𝑒 D)$> ) − 1 𝑒 )&> (𝑒 D)%> ) − 1
−C E−D E\
𝑘F − 𝑘+ 𝑘F − 𝑘,
𝐶*E 𝐶&A
= [𝑘 − 𝑘+ − 𝑘, 𝑒 D)#> − 𝑘+ 𝑒 D)#> − 𝑘+ 𝑒 D)#> − 𝑘+ 𝑒 D)$> 𝐶3 = [𝑘 − 𝑘+ − 𝑘! 𝑒 #."0 − 𝑘+ 𝑒 #.#0 −
𝑘, − 𝑘+ ,
𝑘! − 𝑘+ !
𝑒 D)#> − 𝑒 D)%>
− C𝑘, 𝑘+ D E 𝑒 #."0 − 𝑒 #.(0 𝑒 #.#0 − 𝑒 #.(0
𝑘7 − 𝑘+ S𝑘! 𝑘+ N O − 𝑘! 𝑘+ N OT
𝑒 D)$> − 𝑒 D)%> 𝑘" − 𝑘+ 𝑘" − 𝑘%
− 𝑘, 𝑘+ D EF
𝑘7 − 𝑘F 𝑘" 𝑘! 𝑘+ 𝑒 #."0 − 𝑒 #.)0 𝑒 #.(0 − 𝑒 #.)0
− SN O−N OT −
𝑘7 𝑘, 𝑘+ 𝑒 D)#> − 𝑒 D)&> 𝑒 D)%> − 𝑒 D)&> 𝑘" − 𝑘! 𝑘% − 𝑘+ 𝑘% − 𝑘"
− CD E−D EF
𝑘7 − 𝑘, 𝑘F − 𝑘+ 𝑘F − 𝑘7
𝑘" 𝑘! 𝑘+ 𝑘" 𝑘! 𝑘+ 𝑒 #."0 − 𝑒 #.)0 𝑒 #.(0 − 𝑒 #.)0
𝑘7 𝑘, 𝑘+ 𝑘7 𝑘, 𝑘+ 𝑒 D)#> − 𝑒 D)&> U SN O−N OTX
− ] CD E 𝑘" − 𝑘! 𝑘" − 𝑘! 𝑘% − 𝑘+ 𝑘% − 𝑘"
𝑘7 − 𝑘, 𝑘7 − 𝑘, 𝑘F − 𝑘+
𝑒 D)%> − 𝑒 D)&>
−D EF^
𝑘F − 𝑘7

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