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3BPrieto MP2ChE127
3BPrieto MP2ChE127
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
FIGURE V
CONVERSION VS. TIME AND RATE VS. CONCENTRATION GRAPH FOR
AUTOCATALYTIC REACTIONS
FIGURE VII
TABLE OF VALUES FOR CONVERSION VS. TIME GRAPH
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
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Concentration vs Time Plots; Rates and Reaction Stoichiometry;
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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
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https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Ch
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Microsoft Excel, it was seen how these reactions behave with lex_Reactions
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(n.d.). Retrieved April 9, 2024, from http://the-seventh-
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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
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