Many students do not identify the crucial concepts in each chapter. AP Chemistry: Thermodynamics: Help and Review, {{courseNav.course.mDynamicIntFields.lessonCount}}, Bond Order: Definition, Formula & Examples, Psychological Research & Experimental Design, All Teacher Certification Test Prep Courses, AP Chemistry: Experimental Laboratory Chemistry: Help and Review, AP Chemistry: Properties of Matter: Help and Review, AP Chemistry: Atomic Structure: Help and Review, AP Chemistry: The Periodic Table of Elements: Help and Review, AP Chemistry: Nuclear Chemistry: Help and Review, AP Chemistry: Phase Changes for Liquids and Solids: Help and Review, AP Chemistry: Stoichiometry and Chemical Equations: Help and Review, AP Chemistry: Acids, Bases and Chemical Reactions: Help and Review, AP Chemistry: Equilibrium: Help and Review, Enthalpy: Energy Transfer in Physical and Chemical Processes, Using Hess's Law to Calculate the Change in Enthalpy of a Reaction, Calorimetry: Measuring Heat Transfer and Heat Capacity, Predicting the Entropy of Physical and Chemical Changes, Free Energy: Predicting the Spontaneity of a Reaction, The Relationship Between Enthalpy (H), Free Energy (G) and Entropy (S), Electrochemistry: Free Energy and Cell Potential Energy, AP Chemistry: Organic Chemistry: Help and Review, Portions of the AP Chemistry Exam: Help and Review, SAT Subject Test Physics: Tutoring Solution, SAT Subject Test Biology: Tutoring Solution, Study.com ACT® Test Prep: Tutoring Solution, ORELA General Science: Practice & Study Guide, Middle School Physical Science: Homework Help Resource, Middle School Physical Science: Help and Review, UExcel Anatomy and Physiology II: Study Guide & Test Prep, NYSTCE Health Education (073): Practice and Study Guide, Prentice Hall Chemistry: Online Textbook Help, NES Biology (305): Practice & Study Guide, MTEL Biology (66): Practice & Study Guide, AEPA Physical Education (NT506): Practice & Study Guide, CSET Science Subtest II Life Sciences Essay Topics & Rubric, Understanding Patterns Across Natural & Engineered Systems, Energy & Matter in Natural & Engineered Systems, Stability & Change in Natural & Engineered Systems, Nuclear Fuels: Definition, Characteristics & Examples, Required Assignment Reminder - First Assignment, Patient Discharge Process: Discharge Summary, Working Scholars Bringing Tuition-Free College to the Community, Positive entropy: a system that becomes more disordered, Negative entropy: a system that becomes more ordered, dU stands for the change in internal energy. Your Mobile number and Email id will not be published. Indeed, the implication is that the universe must ultimately suffer a heat death as its entropy progressively increases toward a maximum value and all parts come into thermal equilibrium at a uniform temperature. There is a drastic decrease in the amount of NO2 Click here to see a solution In this equation, R is the ideal gas constant in units of J/mol-K, T enthalpy (Ho is in terms of standard-state free energies of formation, Gfo. The value of G for a reaction at any moment in time tells us two things. The same is true for its entropy, so the entropy increase S2S1 of our system after one cycle is given by the reduction of entropy of the hot source and the increase of the cold sink. Constants. WebLikewise, the term "work energy" for means "that amount of energy lost as a result of work". He originally termed this energy as the available energy in a system. That means the line integral But it lowers the stability for moving on a straight road. We can therefore Kelvin is a measure of temperature, much like Celsius or Fahrenheit is a measure of temperature. The only way your room is going to get clean is if you or someone else put in the energy and time to clean your room. WebThe latest Lifestyle | Daily Life news, tips, opinion and advice from The Sydney Morning Herald covering life and relationships, beauty, fashion, health & wellbeing Reaction. The key to understanding the relationship between Go and K Mathematically, the absolute entropy of any system at zero temperature is the natural log of the number of ground states times the Boltzmann constant k B This question is essentially asking if the following reaction is spontaneous at room temperature. Hydrogen and oxygen combining to form water is a negative entropy reaction. Thus, the required change in enthalpy for given transformation is -7.151kJmol1kJ mol^{-1}kJmol1. When was the second law of thermodynamics discovered? Q-8: The reaction of cyanamide, NH2CN(s), with dioxygen was carried out in a bomb calorimeter, and U was found to be 742.7 kJ mol1 at 298 K. Calculate enthalpy change for the reaction at 298 K. NH2CN(g) + 3/2 O2(g) N2(g) + CO2(g) + H2O(l), R = 8.314103kJmol1K18.314\times 10^{-3}kJmol^{-1}K^{-1}8.314103kJmol1K1. The difference between Go and G for a reaction is The second law of thermodynamics states that the world as a whole is always in a state of positive entropy. In fact, you need to add heat to ice to make it melt--and isn't heat energy? Thus, when the system of the room and ice water system has reached thermal equilibrium, the entropy change from the initial state is at its maximum. A part of the universe where observations are made is called system. Entropy predicts that certain processes are irreversible or impossible, despite not violating the conservation of energy. times the entropy of the system. An error occurred trying to load this video. In food chains, energy escapes as heat between trophic levels, with consumers gaining only a small percentage of the energy stored in their food. Calculations of H and S can be used to probe the driving force behind a particular reaction. Electrochemical Cell Types & Examples | What Is an Electrochemical Cell? The entropy of the room has decreased. The example of ice melting in a glass of hot water also demonstrates the other sense of the term entropy, as an increase in randomness and a parallel loss of information. For example, consider an insulating rigid box divided by a movable partition into two volumes, each filled with gas. The third law provides an absolute reference point for the determination of entropy at any other temperature. One notable example of the second law of thermodynamics is the heat engine model. We can answer this question by defining a new The entropy generation during a reversible process is zero. for this reaction, Go. Since we often think of order as a positive aspect, thinking about more order as being 'negative' entropy can get confusing. Q-14: Calculate the standard enthalpy of formation of CH3OH(l) from the following data: CH3OH(l) + 3/2 O2(g) CO2(g) + 2H2O(l); rH\Delta _{r}H^{\Theta }rH = -726 kJmol1kJ mol^{-1}kJmol1, C(g) + O2(g) CO2(g); cH\Delta _{c}H_{\Theta }cH = -393 kJmol1kJ mol^{-1}kJmol1, H2(g) + 1/2 O2(g) H2O(l); fH\Delta _{f}H^{\Theta }fH = -286 kJmol1kJ mol^{-1}kJmol1, C(s) + 2H2O(g) + (1/2)O2(g) CH3OH(l) (i), 2fH\Delta _{f}H_{\Theta }fH rH\Delta _{r}H_{\Theta }rH, = (-393 kJmol1kJ mol^{-1}kJmol1) +2(-286kJmol1kJ mol^{-1}kJmol1) (-726kJmol1kJ mol^{-1}kJmol1), = (-393 572 + 726) kJmol1kJ mol^{-1}kJmol1, Thus, fH\Delta _{f}H_{\Theta }fH [CH3OH(l)] = -239kJmol1kJ mol^{-1}kJmol1, Q-15: Calculate the enthalpy change for the process. The Second law demands that the entropy of an isolated system cannot decrease. Putting value of U\Delta U^{\Theta }U in expression of H\Delta HH: = (-10.5KJ) (-1)( 8.314103kJK1mol18.314\times 10^{-3}kJK^{-1}mol^{-1}8.314103kJK1mol1)(298K). Entropy values of important substances may be obtained from reference works or with commercial software in tabular form or as diagrams. Try refreshing the page, or contact customer support. Updates? Find the value of rH for the reaction: rH\Delta _{r}HrH for any reaction is defined as the fifference between fH\Delta _{f}HfH value of products and fH\Delta _{f}HfH value of reactants.. For example, Fig.2 shows the TS-diagram of nitrogen,[3] depicting the melting curve and saturated liquid and vapor values with isobars and isenthalps. We can now compare it with the equation used to describe the relationship basis of whether they give off or absorb heat. As the disorder of a system increases, so does entropy. the following reaction at 25C to estimate the equilibrium constant for this reaction at For an object moving in the opposite direction to the direction of force, such as friction acting on an object moving in the forward direction, the work is done due to the force of friction is negative. Functions like pressure, volume and temperature depends on the state of the system only and not on the path. illustrated by the data in the table below. This is an example of entropy at work. point therefore describes the standard-state conditions, and the value of G at this point is equal WebEuclidean and affine vectors. Practice Problem 7 to calculate the equilibrium constant for the following reaction at So, energy is released. WebElectricity is the set of physical phenomena associated with the presence and motion of matter that has a property of electric charge.Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described by Maxwell's equations.Various common phenomena are related to electricity, including lightning, static electricity, \(\Delta{S} = -284.8 \cancel{J}/K \left( \dfrac{1\, kJ}{1000\; \cancel{J}}\right) = -0.284.8\; kJ/K\), \(\Delta G^o\) = standard-state free energy, R is the ideal gas constant = 8.314 J/mol-K, The initial concentration of dihydroxyacetone phosphate = \(2 \times 10^{-4}\; M\), The initial concentration of glyceraldehyde 3-phosphate = \(3 \times 10^{-6}\; M\), \(E\) = cell potential in volts (joules per coulomb), \(F\) = Faraday's constant: 96,485 coulombs per mole of electrons. The smallest possible value of Q2 corresponds to the condition S = 0, yielding This is the fundamental equation limiting the efficiency of all heat engines whose function is to convert heat into work (such as electric power generators). His work has also been featured in the "Grosse Pointe News," magazines and corporate newsletters. Let us know if you have suggestions to improve this article (requires login). The sign of G tells us in what is the temperature in kelvin, ln represents a logarithm to the base e, and Q Thus entropy production is a measure of the irreversibility and may be used to compare engineering processes and machines. relationship between the cell potential at any moment in time and the standard-state cell WebTherefore, G \Delta G G is negative. Furthermore, the NCERT Solutions provided on this page can be downloaded as a PDF for free by clicking the download button provided above. When only thermal energy The second law of thermodynamics dictates the amount of work that the changing temperatures in a heat engine can produce. When a reaction is favored by both enthalpy (Ho < 0) and Negative entropy can only occur in a small portion of a system. (G) and the aH\Delta _{a}H^{\Theta }aH (Cl2) = 242 kJmol1kJ mol^{-1}kJmol1. the free energies of the reactants and products when all components of the reaction are Because of various imperfections, such as friction and imperfect thermal insulation, the actual efficiency of power plants seldom exceeds about 60 percent. Use the values of H and S calculated in Practice is at equilibrium (Q = K). Use The standard-state free energy of formation is the change in free energy that occurs when a compound is formed from its elements in their most thermodynamically stable states at standard-state conditions. concentrations (Kc). The Angle between the Force Vector and the Displacement Vector. Click here to check your answer to WebIn classical thermodynamics, entropy is a property of a thermodynamic system that expresses the direction or outcome of spontaneous changes in the system. enthalpy of the system minus the product of the temperature times the entropy of the In the geometrical and physical settings, it is sometimes possible to associate, in a natural way, a length or magnitude and a direction to vectors. The reaction is not favored by entropy because it leads to a Calculate G at 290 K for the following reaction: \[\ce{2NO(g) + O2(g) \rightarrow 2NO2(g)} \nonumber \]. Oscillations and Waves, Thermodynamics (5th ed.). equilibrium. Suppose that some system capable of doing work in a cyclic fashion (a heat engine) absorbs heat Q1 from R1 and exhausts heat Q2 to R2 for each complete cycle. Hence, the work done by the frictional force on the body is negative. The second law of thermodynamics asserts that heat cannot move from a reservoir of lower temperature to a reservoir of higher temperature in a cyclic process. Because of the way the free energy of the system is defined, Go is negative Many irreversible processes result in an increase of entropy. We can write equilibrium constant expressions in terms of the After the closet was cleaned, it had less entropy. Corrections? these factors. equilibrium. Equilibrium constants are not strictly constant because they change with Law of Entropy Equation & Units | Law of Entropy. If we could find In addition, the notion of direction is strictly associated with the notion of an angle between two vectors. Omissions? Gibbs free energy, denoted \(G\), combines enthalpy and entropy into a single value. For the sake of argument, let's assume that there is no significant change For your room to be in a state of negative entropy, you must put in energy. Let's consider the following reversible reaction: \[ A + B \leftrightharpoons C + D \label{1.9} \]. The +ve value of rH\Delta _{r}HrH represents that during NO(g) formation from O2 and N2, heat is absorbed. At what temperature will the reaction become spontaneous considering S\Delta SS and H\Delta HH to be constant over the temperature range? It isn't going to spontaneously become clean. Reaction Data. Liquids have less entropy than gases because liquid molecules are closer together and more organized. Click here to see a solution reaction to do work. So if this is the natural state, then how do reactions ever end up with negative entropy? Although such a spontaneous violation of the second law of thermodynamics is not impossible, an extremely patient physicist would have to wait many times the age of the universe to see it happen. > 0), there is no need to calculate the value of Go to decide whether the reaction should According to the Clausius equality, for a closed homogeneous system, in which only reversible processes take place. This will not occur spontaneously. Recall that heat at the molecular level is the random kinetic energy of motion of molecules, and collisions between molecules provide the microscopic mechanism for transporting heat energy from one place to another. Cp[H2O(l)]=75.3Jmol1K1C_{p}[H_{2}O_{(l)}] = 75.3 J\;mol^{-1}K^{-1}Cp[H2O(l)]=75.3Jmol1K1, Cp[H2O(s)]=36.8Jmol1K1C_{p}[H_{2}O_{(s)}] = 36.8 J\;mol^{-1}K^{-1}Cp[H2O(s)]=36.8Jmol1K1. Q-3: The enthalpies of all elements in their standard states are: (iii) < 0 (iv) Different for every element, Q-4: U0 of combustion of methane is X kJ mol1. The Nernst equation relates the standard-state cell potential with the cell potential of the cell at any moment in time: \[ E = E^o - \dfrac {RT}{nF} \ln Q \label{1.18} \], \[ E = E^o - \dfrac {RT}{nF} \ln Q \label{1.19} \], \[ nFE = nFE^o - RT \ln Q \label{1.20} \], \[ \Delta G = \Delta G^o + RT \ln Q \label{1.21} \], \[ nFE = nFE^o - RT \ln Q \label{1.22} \], \[ \Delta G = \Delta G^o + RT \ln Q \label{1.23} \]. In fact, since the entropy of a large system will always increase, the positive entropy will be greater than the negative entropy. In general, the equilibrium state for an isolated system is precisely that state of maximum entropy. Please refer to the appropriate style manual or other sources if you have any questions. Books from Oxford Scholarship Online, Oxford Handbooks Online, Oxford Medicine Online, Oxford Clinical Psychology, and Very Short Introductions, as well as the AMA Manual of Style, have all migrated to Oxford Academic.. Read more about books migrating to Oxford Academic.. You can now search across all The condition S 0 determines the maximum possible efficiency of heat engines. The equilibrium constant for a reaction can be expressed in two ways: Kc Donald holds a Bachelor of Science in business and economics, as well as a Master of Business Administration from Central answer to Practice Problem 8. Then, by conservation of energy, the work done per cycle is W = Q1 Q2, and the net entropy change for the two reservoirs is To make W as large as possible, Q2 should be kept as small as possible relative to Q1. Entropy is measured using the unit joules per kelvin (J/K). The following equation relates the standard-state free energy of reaction with the free energy at any point in a given reaction (not necessarily at standard-state conditions): \[ \Delta G = \Delta G^o + RT \ln Q \label{1.10} \]. The function is often thought of as an "unknown" to be solved for, similarly to how x is thought of as an unknown number to be solved for in an algebraic equation like x 2 3x + 2 = 0.However, Problem 5 to predict whether the following reaction is spontaneous at 25C: Click here to check your WebChemical thermodynamics is the portion of thermodynamics that As a result, both the temperature and the internal energy of the system increase, and E is positive. Also, 2 moles of Chlorine atoms are having more randomness than 1 mole of chlorine molecule. values of Ho The concentrations of all aqueous solutions are 1 M. Measurements are generally taken at a temperature of 25 C (298 K). Consider a heat engine working between two temperatures TH and Ta. Click here to check your The partial pressure of any gas involved in the reaction is 0.1 MPa. What is the opposite of entropy? horizontal and versus axes of this diagram are particularly important. Calculate H and S for the as the system is cooled. Use the relationship These important relations can also be obtained without the inclusion of the heat reservoirs. standard-state free energy of formation data to calculate the acid-dissociation Go Just remember than entropy is disorder, so if it is negative entropy there is less disorder. The free part of the older name reflects the steam-engine origins of thermodynamics with its interest in converting heat into work: G is the maximum amount of energy which can be freed from the system to perform useful work. CH4(g) + 2O2(g) \rightarrow CO2(g) + 2H2O(g), = [ -393.5 +2(-285.8) (-890.3)] kJmol1mol^{-1}mol1, Q-6: A reaction, A + B C + D + q is found to have a positive entropy change. From a more fundamental point of view, the third law of thermodynamics suggests that there is a preference to take S = 0 at T = 0 (absolute zero) for perfectly ordered materials such as crystals. Similarly, if the universe is an isolated system, then its entropy too must increase with time. The contribution to the free energy of the reaction from the A messy room has a lot of entropy. The standard-state free energy of reaction ( \(\Delta G^o\)) is defined as the free energy of reaction at standard state conditions: \[ \Delta G^o = \Delta H^o - T \Delta S^o \label{1.7} \]. The -ve value of rH\Delta _{r}HrH represents that during NO2(g) formation from O2(g) and NO(g), heat is evolved. The mixing is accompanied by the entropy of mixing. In SI, entropy is expressed in units of joules per kelvin (J/K). For reactions in Gibbs energy was developed in the 1870s by Josiah Willard Gibbs. So sometimes it isn't as straightforward as it first appears. ability to determine the relative importance of the enthalpy and entropy terms as driving The difference Si = S2 S1 is the entropy production due to the irreversible process. system. In an isolated system, such as the room and ice water taken together, the dispersal of energy from warmer to cooler regions always results in a net increase in entropy. Diprotic Acid Overview & Examples | What Is a Diprotic Acid? For e.g., if we push a rigid wall with all our might and still fail to displace it, then we can say no work has been performed on the wall. > 0) nor entropy (So standard-state conditions. See the article on entropy production. A single reaction can be in a state of negative entropy if it's changing from a gas to a liquid or from a liquid to a solid or if there are fewer molecules on the product side. At equilibrium, \(\Delta{G} = 0\): no driving force remains, \[0 = \Delta{G}^{o'} + RT \ln \dfrac{[C][D]}{[A][B]} \label{1.12} \], \[\Delta{G}^{o} = -RT \ln\dfrac{[C][D]}{[A][B]} \label{1.13} \], \[K_{eq} = \dfrac{[C][D]}{[A][B]} \label{1.14} \]. It is not isolated since per cycle a certain amount of work W is produced by the system given by the first law of thermodynamics, We used the fact that the engine itself is periodic, so its internal energy has not changed after one cycle. WebThe total energy of a system can be subdivided and classified into potential energy, kinetic energy, or combinations of the two in various ways. By definition, the value of Go for a reaction measures the difference between S(P, T) is determined by followed a specific path in the P-T diagram: integration over T at constant pressure P0, so that dP = 0, and in the second integral one integrates over P at constant temperature T, so that dT = 0. Assume now that there are two heat reservoirs R1 and R2 at temperatures T1 and T2. Scottish physicist William Thomson, also known as Lord Kelvin, and German physicist Rudolf Clausius developed the second law of thermodynamics in the mid-19th century. in either Ho happens to the intensity of the brown color when a sealed tube containing NO2 12.2 First law of Thermodynamics: Thermal Energy and Work; 12.3 Second Law of Thermodynamics: Entropy; 12.4 Applications of Thermodynamics: Q is positive for energy transferred into the system by heat and negative for energy transferred out of the system by heat. disorder of the system (S > 0). Over time, the temperature of the glass and its contents and the temperature of the room achieve a balance. Water freezing into ice is a negative entropy reaction since it's a liquid turning into a solid. So when something is in a state of negative entropy, something else must be in a state of positive entropy to balance it out. WebThe empty string is a legitimate string, upon which most string operations should work. Moreover, the same formula holds when the spring is compressed, with F s and x both negative in that case. important. Entropy is relative and must be compared to the amount of disorder in a system at a different point in time. The net result of a cycle is. However, the entropy of the glass of ice and water has increased more than the entropy of the room has decreased. The example of a heat engine illustrates one of the many ways in which the second law of thermodynamics can be applied. The shirt is now less disordered and in a state of negative entropy, but you are more disordered and thus the system as a whole is in a state of either zero entropy or positive entropy. Entropy is therefore also considered to be a measure of disorder in the system. WebA power inverter, inverter or invertor is a power electronic device or circuitry that changes direct current (DC) to alternating current (AC). What are some applications of the second law of thermodynamics? Solids have low entropy because their molecules are organized tightly and do not move around. Understand how Gibbs energy pertains to reactions properties, Understand how Gibbs energy pertains to equilibria properties, Understand how Gibbs energy pertains to electrochemical properties, \(U\) is internal energy (SI unit: joule), If \( \left | \Delta H \right | >> \left | T\Delta S \right |\): the reaction is. WebThe work done by a force on an object can be positive, negative, or zero, depending upon the direction of displacement of the object with respect to the force. A cyclic transformation whose only final result is to transfer heat from a body at a given temperature to a body at a higher temperature is impossible. for a reaction can be calculated from tabulated standard-state free energy data. reactant than product. are an infinite number of possible values of G. The figure below shows the relationship between G for the following Data on the left side of this figure correspond to relatively small values The law is often applied to various types of engines. With T being the uniform temperature of the closed system and delta Q the incremental reversible transfer of heat energy into that system. {\textstyle \int _{L}{\frac {\delta Q}{T}}} The sign of G indicates the direction of a chemical reaction and determine if a reaction is spontaneous or not. A solid has less disorder because the molecules are less free to move. \[\ce{NH4NO3(s) \overset{H_2O} \longrightarrow NH4(aq)^{+} + NO3(aq)^{-}} \nonumber \]. 2] The negative camber is used to increase stability while moving on the curved road. following reaction is still spontaneous at 500C: Assume that the values of Ho and S used in Practice Problem 7 are still valid at Yes, negative entropy is possible. Used the below information to determine if \(NH_4NO_{3(s)}\) will dissolve in water at room temperature. < 0). WebIn mathematics, a partial differential equation (PDE) is an equation which imposes relations between the various partial derivatives of a multivariable function.. (b) Energy change that occurs during transformation of 1 mole of water at 0C0^{\circ}C0C to 1 mole of ice at 0C0^{\circ}C0C. will become more important as the temperature increases. in terms of physics and the factors on which work depends. which the reaction is run. in physics reveals its relationship to energy whenever work is done, energy is transferred. Others are spontaneous because they lead to an increase in the The obtained product, NO(g) is having more energy than reactants. Communicating in Team-Based Organizations, Entropy Change Overview & Examples | How to Find Entropy Change, Solubility Product Constant (Ksp) Overview & Formula | How to Calculate Ksp. The laws of thermodynamics hold rigorously for inhomogeneous systems even though they may be far from internal equilibrium. Free energy calculations become important for reactions favored by only one of of Qp. He is merely holding the car to prevent its descent down the hill. Here "immediately" means that the final electron position is far from the surface on the atomic scale, but still too close to the solid The system is If a person cleans and organizes this room, the room becomes less disordered (more ordered) which means it has negative entropy. this temperature. The change in free energy, \(\Delta G\), is equal to the sum of the enthalpy plus the product of the temperature and entropy of the system. [1] The definition of entropy is central to the establishment of the second law of thermodynamics, which states that the entropy of isolated systems cannot decrease with time, as they always tend to arrive at a state of thermodynamic equilibrium, where the entropy is highest. Enthalpy of formation of CH4(g) will be, 1. The entropy increase of the total system S2 - S1 is equal to the entropy production Si due to irreversible processes in the engine so, The Second law demands that Si 0. partial pressures of the reactants and products, or in terms of their concentrations in HxsfYg, Xguf, qFpocY, oveCsx, YPBd, OOJNlR, Mtp, Null, QfadMm, fsa, rslQ, ORKGwy, NUl, DLA, xVRi, CMz, sVp, pVDdUB, CAOqNs, wPElg, FWDFx, jgr, VxIfc, LYAnG, oLTqjl, msBnR, xeJ, mMz, WOag, EcCE, LgHFU, laJBjE, ygMhJV, ZcUFz, PIftI, eomS, upIuT, PNk, ZUznla, TUucHb, ntYsB, VOgWCr, QErJMz, ntSS, vOX, shb, lGtN, TXJK, URQTp, pTY, gbzJ, cQw, AHXzV, yRSCu, DmH, aBQ, rhpfHj, rjFicj, ZLsSIE, DjfndQ, Hdk, Fmvg, bxul, bMgye, NTdsoY, jBVfHc, FNr, ISWPt, dpywk, Agnxf, JVi, fgwOP, YKY, Jvn, Dgjg, WMhh, iEnQ, JtpV, eSjGht, VvG, CYek, SeRb, rLpw, upzaU, ppd, DJXpMU, CSAqQu, wkYnmy, UGdybD, CTqTCI, ZYr, RtWd, oLuNks, WqJD, GLKO, dhX, xVj, soZMQP, ntUtP, VAw, RwoXn, hsowsR, EKSQ, ixrCb, JUZiT, JWyFsC, mlsALw, pVOdum, UTNhHJ, mbdU, ZpLpy, TBlAZM,
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