Questions tagged [thermodynamics]

Applicable to questions about heat, energy, work, and their interconversion in chemistry. See the tag wiki for a detailed list of topics. Questions tagged may also be tagged with [enthalpy], [energy], [free-energy] where appropriate.

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4
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3answers
151 views

Calculating ΔG at the extremes of reaction extent

This question follows on from a great post on comparing $\Delta_\mathrm{r} G^{\circ}$ to $\Delta_\mathrm{r} G$ answered here The G vs ξ graph that is used in the answer is an excellent tool to ...
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1answer
34 views

Can somebody explain the low temperature Schottky anomaly for two level systems?

Statistical thermodynamics question. Can somebody explain the low temperature Schottky anomaly for two level systems? Why is this anomaly not seen in all materials?
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3answers
355 views

If change in free energy (G) is positive, how do those reactions still occur?

I was doing a couple of problems for homework: Calculate $K_\mathrm{sp}$ of $\ce{AgI}$ at $55.0\ \mathrm{^\circ C}$ Calculate $K_\mathrm{b}$ of $\ce{NH3}$ at $36.0\ \mathrm{^\circ C}$ I have to use ...
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0answers
40 views

Gibbs free energy of activation and activation energy [duplicate]

What the difference between Gibbs free energy of activation and activation energy
0
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0answers
34 views

Calculating melting temperature of water with thermodynamical data

So at zero degrees celsius($\pu{273 K}$), for clean water, we have the equilibrium eq.: $\ce{H2O(s) = H2O(l)}$ As it is at equilibrium, we know that $\Delta G = 0$. As we are dealing with clean ...
5
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2answers
64 views

Is temperature double-counted in the Gibbs free energy equation?

Complete amateur here. When looking at one form of the equation deriving the change in Gibbs free energy for a given chemical reaction, the terms change in enthalpy, and the negative product of ...
2
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1answer
46 views

Thermodynamics behind organic chemical reactions? [closed]

I took organic chemistry a few years ago at my university, and although I went through the motions to pass the exams, I didn't understand the thermodynamic reasoning behind why the reactions actually ...
1
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1answer
86 views

Why do we use external pressure when calculating work done by gas? [duplicate]

For irreversible expansion and compression, why is dw= -pextdV but not dw= -pdV ? Many of the texts and related questions on this site I encountered give a same general idea: because work done= ...
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1answer
50 views

Entropy and total differential

In an exercise, I have derived that $$\mathrm dS_\mathrm{m} = \frac{3R}{2T}\mathrm dT + \frac{R}{V}\mathrm dV$$ using the 1st and 2nd law of thermodynamics (1 mol ideal gas). Now, I want to write $\...
2
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0answers
56 views

Given Kd find equilibrium concentrations of the reactants

$$\ce{Biotin + Avidin → Complex}$$ Biotin is a vitamin derivative that binds extremely tightly to avidin (a protein found in egg white) with a $K_\mathrm{d}$ of $\pu{1e-15 M}$. If you make a ...
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0answers
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Correct Generalization for Adair Equation?

I know how to derive the Adair Equation for n binding sites the long way, writing n+1 mini equations and linking them to relate all sub $K_b$ values to $K_{b-intrinsic}$. Tried to find a general ...
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2answers
68 views

Relation between ΔH and ΔE for the reaction in gaseous phase at constant temperature and pressure

Which of the following statements is correct for the reaction at constant temperature and pressure: $$\ce{CO(g) + \frac{1}{2}O_2(g) -> CO2(g)}$$ $\Delta H = \Delta E$ $\Delta H > \...
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0answers
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Trying to understand rationale behind Joule-Thomson experiment

The purpose of the original Joule (as opposed to JT) expansion experiment was to assess intermolecular interactions in real gases. In that experiment, Joule immersed twin glass globes into a water ...
2
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1answer
82 views

Negative Molar Specific Heat of a Gas

It is known that the specific heat of a gas is process dependent. So it must be theoretically possible to have a negative value for a gas according to the following equation (for polytropic process, $...
3
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1answer
83 views

Current and reversible heat in battery reaction

In the book Battery Technology Handbook by Kiehne [1] (Google Books) on page 21, equation (32): The reversible heat effect per time unit can be related to current flow, because each multiple of the ...
3
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2answers
138 views

Energy balance in battery thermodynamics

I am trying to understand the derivation of a general energy balance in battery thermodynamics. The following relation is frequently found to determine the heat generation of a battery: $\dot{Q} = \...
3
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2answers
64 views

How to measure quantities at standard state when this state is a hypothetical one?

Consider the reaction $$\ce{A(g) + H2O(l) <=> B(aq) + C(g)}$$ If all gases and solutions were ideal, the standard state would be pure water, the solute B at a concentration of 1 M, the gases A ...
1
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1answer
36 views

Change in heat of photosynthesis

Consider a plant that uses the energy it receives from the sun to do work (to undergo photosynthesis) to produce glucose. The minimum amount of work this plant can do to produce 1 mole of glucose is ...
2
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1answer
95 views

Gibbs Free Energy Notation

What's the difference between $G$, $\Delta G$, $\Delta G^\circ$, and $\Delta_\mathrm r G^\circ$? I've seen the first two used interchangably, and seen $G$ specifically referred to as change in Gibbs ...
1
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1answer
19 views

Which quantities change when choosing a different standard state?

Chemistry and biochemistry use a different standard state. For example, the standard hydrogen ion concentration is the one at pH = 0 in one case, and the one at neutral pH in the other case. Which ...
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0answers
30 views

Derivation of relationship betwee standard Gibbs energy of reaction and equilibrium constant? [closed]

How does one derive $\Delta_\mathrm r G^\circ = -RT\ln(K)$? I don't see the connection mathematically or conceptually; how does Gibbs at all relate to the equilibrium constant of a reaction? This was ...
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1answer
79 views

Why does the derivation Gibbs-Helmholtz equation hold when the enthalpy is temperature-dependant

The derivation shown here assumes H and U are independant of temperature, right? But what if $H(T) = H_{0}+C_V \Delta T $? Then $dG = C_V\, dT - SdT$, right? So $ \displaystyle \left( \frac{\partial ...
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0answers
39 views

Calculate the energy in the form of heat (in kJ) required to convert 325 grams of liquid water at 20.0 °C to steam at 115 °C

Calculate the energy in the form of heat (in kJ) required to convert 325 g of liquid water at 20.0 °C to steam at 115 °C. Assume that no energy in the form of heat is transferred to the environment. (...
0
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1answer
47 views

How to calculate dew point of air-water system

I want to calculate the maximum water holding capacity of air at a given temperature (as in $\frac{max\ mass\ of\ water}{mass\ of\ dry\ air} $ vs temperature) I looked up online and there are ...
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0answers
25 views

Impact of pH? Change in Binding Affinity of protein-ligand complex based on pH and Kd?

When the $\mathrm{pH}$ was $5.0$, the temperature was $\pu{25 °C}$,the $K_\mathrm{D}$ was $\pu{5 μM}$, and [L] was equal to $K_D$, the protein(s) were half bound. Question considers half bound ...
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1answer
30 views

Chemical Equilibria - Fraction Bound equation based on Kd, [R], [L], [RL], is actually an average?

Let's say 150 stem cells express exactly 150 copies of the same mebrane antigen X. While all differentiated cells express exactly 15 copies of X. To the cell mixture you add a large amount of 0.2 μM ...
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2answers
40 views

Enzyme Kinetics - Given Km find substrate concentration at a certain velocity

From what I understand about the Michaelis Menten Model Km defines the amount of substrate required to reach half-saturation. 1/2 Vmax corresponds to Km on the x axis Generic formula is v = Kcat [...
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2answers
53 views

Thermodynamics - Series Reaction - Estimating mols of reactants based on Free Energy of Rxn

Question Three reactions occur simulteneously (assume ideal) at $\pu{T = 0^\circ C}$. $$\ce{A<=>B<=>C<=>D}$$ a) With $\Delta_r G^\circ_\text{AB} = \pu{400 J/mol}$, $\...
8
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1answer
235 views

Based on their respective number of degrees of freedom, what's the most efficient fuel; hydrogen or gasoline?

The reaction of octane's combustion is: $$\ce{2 C8H18 + 25 O2 -> 18 H2O + 16 CO2}$$ I am asked for computing the number of degrees of freedom of the octane given that its specific heat is $\pu{...
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0answers
22 views

why is white phosphorous given to have ZERO standard heat of formation [duplicate]

why is white phosphorous given to have ZERO standard heat of formation?? while it is well known fact that white phosphorous is highly reactive and is obviously less stable than red and black ...
5
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2answers
290 views

How to solve constants out of the internal energy equation?

Imagine we deal with a new kind of matter, whose state is described by: $$PV = AT^3$$ Its internal energy is given by $$U = BT^n \ln\left(\frac{V}{V_0}\right) + f(T)$$ where $A$, $...
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1answer
64 views

Do electrons go to even lower ground states after exothermic reactions?

I am a bit confused about what happens to the energy levels during an exothermic reaction. I understand that during an exothermic reaction, the energy of the electrons decreases. Is the potential ...
0
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1answer
45 views

What is meant by excess energy in exothermic reaction?

I was reading this article on exothermic reactions online: Exothermic reactions It states that "In exothermic reactions, the products have less enthalpy than the reactants, and as a result, an ...
4
votes
1answer
277 views

Would the change in enthalpy (ΔH) for the dissolution of urea in water be positive or negative?

To test the properties of a fertilizer, $15.0\ \mathrm g$ of urea, $\ce{NH2CONH2(s)}$, is dissolved in $150\ \mathrm{mL}$ of water in a simple calorimeter. A temperature change from $20.6\ \mathrm{^\...
1
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1answer
69 views

Temperature dependency of enthalpy H and entropy S [closed]

In textbooks, I often read that the temperature dependency of the enthalpy of reaction $\Delta_\mathrm{r}H$ and the entropy of reaction $\Delta_\mathrm{r}S$ can be neglected (in a limited $T$-range). ...
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0answers
28 views

Simplifying temperature profile

I am given the temperature profile below and the two equations: $$Q = (2\pi R_0)LU_0(T_{1\infty}-T_{2\infty})\tag1\label1$$ $$\frac{1}{U_0R_0} = \frac{1}{h_1R_0} +\frac{\ln(R_\mathrm a/R_0)}{k}+ ...
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0answers
50 views

Why is the reaction quotient Q always equal to one at standard state?

I understand that at equilibrium, $Q$ is equal to $K$. This should not depend how I express concentrations (as amount of substance concentrations $c$ or as partial pressures $p$ or as molality $b$ or ...
0
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1answer
73 views

How should we express concentrations and partial pressures in ΔG=-RTlnK? [duplicate]

I understand that $K$ will be dimensionless. Let's say an equilibrium involving $K_p$ and the reaction is $\ce{A -> B}$, $K_p$ will be dimensionless. If the reaction $\ce{A + B -> C}$, then ...
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0answers
24 views

Isobaric-isothermal ensemble with degeneracy

I've been studying statistical mechanics for a while, the topic is very far from what I've learned till now so my questions may be superficial. When trying to see what my entropy is in an isobaric-...
-2
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1answer
46 views

Are these calculations valid enough? [closed]

I am not able to understand how these calculations are being done in this book. Up until this section, the book is going smoothly. However, how are these calculations accountable? If anyone can ...
2
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1answer
73 views

Proving a relation for fugacity of component i in term of independent variables (T,V)

In Molecular Thermodynamics of fluid phase equilibria by Prausnitz et al. [1] the authors recommend to use the following equation which gives the fugacity of component $i$ in terms of independent ...
6
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1answer
122 views

Contribution of vibrational degrees of freedom

The ratio $\displaystyle\frac{C_p}{C_v}$ for linear triatomic molecules including vibration contribution is given by: ? Attempt: We are aware that $C_v = \frac{fR}{2}$ and $C_p = C_v+ R$ Hence, $\...
2
votes
1answer
125 views

Gibbs Free Energy and Maximum Work

I am a high school student and my professor mentioned that the Gibbs free energy is the maximum amount of work (or useful work) that a system can do, whereas entropy is a measure of the non-available ...
27
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2answers
6k views

When a candle burns, why does the top of wick glow if bottom of flame is hottest?

Totally an elementary question. Staring at a candle, it appears that the bottom of the wick is dark whereas the top glows. However the bottom of the flame (the blue) is the hottest. Is the reason ...
3
votes
2answers
305 views

Why is my conclusion inconsistent with the van't Hoff equation?

Let's say I hypothesize that a graph of $\ln K$ vs. $1/T$ has a slope of $-∆G^\circ/R$ and a $y$-intercept of $0$. I prove it simply: $$∆G^\circ = -RT\ln K \quad\to\quad \ln K = -\frac{∆G^\circ}{RT}$$...
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0answers
29 views

Hydrogen peroxide and carbon as hybrid rocket propellant?

I was thinking that a hybrid rocket could be made using hydrogen peroxide and activated charcoal or some other carbon source. Step 1: Decompose hydrogen peroxide to steam and oxygen, as in a ...
7
votes
2answers
498 views

Cp vs Cv for liquid water @ < 4 °C

I'm looking at a textbook question (Engel & Reid, Thermodynamics, Statistical Thermodynamics & Kinetics, 4 ed, Q3.1) which states the following: The heat capacity $C_{\mathrm m,p}$ is less ...
0
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1answer
47 views

Calorimetry: Temperature Increase due to stirring of reactants

I am not yet in university, but I hear a common first-year chemistry lab/practical is to do calorimetry taking into consideration the small (and usually negligible) rise in temperature due to the ...
2
votes
1answer
68 views

Change in Gibbs free energy vs. change in enthalpy

When learning about other thermodynamic quantities, like $\Delta H$, I was taught that this represents the energy absorbed or released by a system after the reaction has gone 100% to completion. For ...
14
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3answers
3k views

Is it possible to boil a liquid by just mixing many immiscible liquids together?

In open air, when vapour pressure reaches 1 atm, boiling takes place. I read that if we add two immiscible liquids together, the total vapour pressure of the 'mixture' is close to $p = p^*_A + p^*_b$,...