Questions tagged [physical-chemistry]

The study of chemical systems using the laws and concepts of physics. This usually requires the techniques of thermodynamics, statistical mechanics and quantum mechanics.

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167
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8answers
132k views

Can an atom have more than 8 valence electrons? If not, why is 8 the limit?

According to some chemistry textbooks, the maximum number of valence electrons for an atom is 8, but the reason for this is not explained. So, can an atom have more than 8 valence electrons? If ...
45
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4answers
3k views

Unit of the equilibrium constant: contradiction of Bridgman's theorem?

The following equation is standard in thermodynamics: $$ \Delta G^\circ=-RT\log(K) $$ where $K$ is the equilibrium constant. In dimensional analysis, Bridgman's theorem tells us that the argument ...
29
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2answers
25k views

What exactly is hydrogen bonding (and does it really need fluorine, oxygen, or nitrogen)?

I'm not satisfied with the rationale for the intermolecular attraction known as hydrogen bonding. In my book, it states that Hydrogen bonding is a special type of intermolecular attraction between ...
18
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2answers
955 views

Which equilibrium constant is appropriate to use?

I have learnt that the standard free energy change is related to the equilibrium constant of a reaction by, $$\Delta G^\circ = -RT \ln K$$ Here, does $K$ refer to $K_p$ or $K_c$? Also, please give ...
44
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3answers
297k views

Why is it important to use a salt bridge in a voltaic cell? Can a wire be used?

I was learning about voltaic cells and came across salt bridges. If the purpose of the salt bridge is only to move electrons from an electrolyte solution to the other, then why can I not use a wire? ...
50
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5answers
9k views

The last element's atomic number

I was just thinking what can be the last atomic number that can exist within the range of permissible radioactivity limit and considering all other factors in quantum physics and chemical factors.
47
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6answers
459k views

Positive or Negative Anode/Cathode in Electrolytic/Galvanic Cell

In a galvanic (voltaic) cell, the anode is considered negative and the cathode is considered positive. This seems reasonable as the anode is the source of electrons and cathode is where the electrons ...
7
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3answers
8k views

Can the change in internal energy be nonzero if temperature is constant?

I have learnt that internal energy, $U$, is a state function and it only depends on temperature... So if $\Delta T = 0$ then $\Delta U = 0$. However when I was studying exothermic and endothermic ...
11
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4answers
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Is there a reason for the mathematical form of the equilibrium constant? [duplicate]

Why are the two molarities multiplied and not added, and why is each raised to the power of the coefficient rather than multiplied by it? What is the reasoning behind this form? Was it simply ...
25
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4answers
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Hypothetical: What happens to water as pressure increases to infinity? [duplicate]

I've asked a similar question here but the answer given shows the behaviour of water under general conditions. I'd like to know what the behaviour of water is like as pressures increase towards ...
26
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1answer
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What is the pKa of the hydronium, or oxonium, ion (H3O+)?

Although the wikipedia page on Hydronium indicates a $\mathrm{p}K_\text{a}$ of −1.74, I noticed in the discussion of this page that the subject seems debated (cf. http://en.wikipedia.org/wiki/Talk:...
8
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1answer
303 views

Why do dianions (such as malonate) bind cations more strongly than anions?

Why does a dianion (such as malonate) bind cations more strongly than its equivalent anion (acetate)? Is it simply because of the proximal availability of another $\ce{O-}$ group that can bind to ...
22
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1answer
923 views

While filling electrons, we follow Aufbau principle, but not while removing them. Why is this so?

I recently came across a question Why is the vanadium(3+) ion paramagnetic?, where the asker is wondering how $\ce{V^{3+}}$ is paramagnetic (he used Aufbau in reverse to remove the electrons), while ...
10
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2answers
22k views

Why do 3d orbitals have lesser energy than 4s orbitals in transition metals? [duplicate]

This is quoted from Jim Clark's Chemguide For reasons which are too complicated to go into at this level, once you get to scandium, the energy of the 3d orbitals becomes slightly less than that of ...
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4answers
9k views

Is not possible to find absolute value of internal energy?

Today in thermodynamics lecture my teacher told that it is not possible to find absolute value of internal energy so we have to calculate change in internal energy. So my question is why is it not ...
44
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2answers
12k views

What volume does one mole of an ideal gas occupy?

This has been bugging me for a while now... Obviously, to calculate the volume/space occupied by a mole of (an ideal) gas, you'll have to specify temperature ($T$) and pressure ($P$), find the gas ...
26
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4answers
4k views

Why don't equivalent hydrogens cause splitting in NMR?

When doing NMR spectroscopy, it is an observed fact that equivalent hydrogens do not split one another. Why don't equivalent hydrogens split each other's signals? For example, why is the NMR spectrum ...
19
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1answer
5k views

Why can't helium be solidified at 'ordinary' pressures?

According to the UC Davis ChemWiki Chemistry of Helium, helium has a comparatively unusual property, specifically: Helium is the only element that cannot be solidified by lowering the temperature ...
15
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2answers
24k views

How does volume contraction in solvent mixing work?

I recall seeing chemistry demonstrations where a significant amount of a solute is dissolved in a solvent and the solution volume barely changes. Questions regarding this: 1) How is this possible? 2)...
24
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5answers
14k views

Why does radium have a higher first ionisation energy than barium?

I'm wondering why radium appears to buck the general trend that first ionisation energies decrease as you move down a group in the periodic table: barium (the group 2 element preceding it) has a first ...
21
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3answers
25k views

Why are solids and liquids not included in the equilibrium constant? What about in a reaction rate calculation?

Take for instance the reaction $$\ce{H2(g) + I2(s) <=> 2HI(g)}$$ The equilibrium constant would not include the solid $\ce{I2}$, but why is this? I have read that its concentration is a ...
11
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1answer
1k views

Destabilization of antibonding MO vs stabilization of bonding MO

My textbook writes that The net energy stabilization due to the occupation of a bonding MO is equal to the net energy destabilization due to the occupation of the corresponding antibonding MO. ...
10
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3answers
7k views

How can the equilibrium shift, while Kc remains constant?

Consider the following reversible reaction. $$\ce{Cr2O7^2-(aq) + H2O(l) <=> 2 CrO4^2-(aq) + 2 H+(aq)}$$ What will happen to the position of equilibrium and the value of $K_c$ when more ...
8
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1answer
10k views

How does intramolecular hydrogen bonding cause the molecules to be separated from each other?

I learnt about intramolecular hydrogen bonding today, which occurs between molecules such as ortho-nitrophenol. What I was told is that in case of intramolecular bonding, the molecules separate from ...
8
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1answer
312 views

Why don't we see these lanthanide species?

For most lanthanide metals$^{[1]}$, the stable oxidation state is III. The general electronic structure$^{[2]}$ is $$\ce{[Xe] 4f^{0}^{-14} 5s^2 5p^6 5d^{0}^{-1} 6s^2}.$$ Elements that have the d-...
28
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2answers
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Why is snow white?

I know that this is a rather ambiguous question; but my question is, whenever we take water and freeze it in the freezer, it still tends to stay clear. Since snow is just frozen water, why is it white?...
23
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2answers
3k views

How to find the second order perturbation to wave function?

Today, I'm looking for how to find the 2nd perturbation to the base in Rayleigh Schrödinger Perturbation Theory (RSPT). SETUP Starting from the 2nd order perturbation in Dirac's notation: \begin{...
34
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4answers
8k views

What exactly is happening when sodium, potassium, or other alkali metal explodes in water?

There are lots of videos on YouTube showing sodium, potassium, etc. exploding when dropped into water (this, for example). I understand that when an alkali metal is exposed to water, a violent ...
17
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3answers
81k views

Angular and radial nodes

Nodes are the points in space around a nucleus where the probability of finding an electron is zero. However, I heard that there are two kinds of nodes, radial nodes and angular nodes. What are they ...
21
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2answers
7k views

Derivation of the Heisenberg uncertainty principle

The Heisenberg uncertainty principle states that $$\Delta x \Delta p \geq \frac{\hbar}{2}$$ where $\Delta x$ is the uncertainty in the position, $\Delta p$ is the uncertainty in linear momentum, and ...
27
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1answer
14k views

Electrical conductivity of graphite

On this Wikipedia page, the electrical conductivity of various materials are given in the third column ($\sigma \text{ (S/m) at 20}^\circ \text{C}$). I am interested in the entry for Carbon (graphite)...
8
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2answers
371 views

Ozone is above, nitrogen is below

Ozone is heavier than nitrogen. Then why is ozone in stratosphere and nitrogen in troposphere?
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3answers
837 views

Understanding Beta Decay

Reading Wikipedia on "Beta Decay" they list the equation of Carbon-14 decaying into N-14. see equation https://en.wikipedia.org/wiki/Beta_decay I presume the 14 refers to total protons and neutrons. ...
29
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3answers
924k views

What are the maximum number of electrons in each shell?

In my textbook, it says that the maximum number of electrons that can fit in any given shell is given by 2n². This would mean 2 electrons could fit in the first shell, 8 could fit in the second shell, ...
31
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1answer
7k views

When is it true that more nodes equals higher energy?

Consider all the MOs of some isolated molecule. (It could be a single atom too; I'll use MO to refer to AOs as well.) Number them in increasing order of the number of nodes (node = surface where the ...
28
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2answers
11k views

Confusion about direction of dipole arrow in alpha-helices and other molecules

I understand that molecular dipoles are electric dipoles. And electric dipole moment vectors point from the negative to the positive charge. In class we learned to draw these special molecular dipole ...
30
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5answers
10k views

Why don't the electrons move through the electrolyte (instead of the circuit) in a galvanic cell?

I was learning about galvanic cells and I had a problem understanding why electrons do not travel through the electrolyte solutions themselves, instead preferring to travel through metals. Can ...
24
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1answer
2k views

When can a molecule be considered freely rotating at room temperature?

This question sparked from a long discussion in chat about the nature of $\ce{H2O2}$ and whether that molecule can be considered to rotate around the $\ce{O-O}$ axis (and hence display axial chirality)...
23
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4answers
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Why does water evaporate spontaneously at room temperature despite ΔG > 0?

Standard Gibbs free energy of formation of liquid water at $\pu{298 K}$ is $\pu{−237.17 kJ mol-1}$ and that of water vapour is $\pu{−228.57 kJ mol-1}$ therefore, $$\ce{H2O (l) -> H2O (g)}\qquad\...
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5answers
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Why do branched chain compounds have lower boiling points than the corresponding straight chain isomers?

The branched chain compounds have lower boiling points than the corresponding straight chain isomers. For example, $\ce{CH_3CH_2CH_2CH_2CH_3}$ - No branching-Pentane (n-pentane) ($\mathrm{...
18
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2answers
38k views

How does a lone pair of a central atom affect the dipole moment?

Dipole moment is the degree of polarity, i.e. the seperation of positive and negative charges. But I am not getting the intuition why and how lone pairs affect the polarity and dipole moment. I cannot ...
20
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1answer
5k views

Why is NaCl3 possible?

There. And there. Almost a year ago, a group of scientists claimed to have reached compounds of $\ce{Na}$ and $\ce{Cl}$ with weird stochiometries ($\ce{NaCl3, Na3Cl, NaCl7, Na3Cl2}$ and $\ce{Na2Cl}$). ...
10
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3answers
6k views

Most probable point for finding an electron in the 1s orbital of a Hydrogen atom

My professor says that the most probable point for finding an electron in a 1s orbital of a hydrogen atom is at its origin. He explains this by citing the fact that the square of the wave function ...
16
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4answers
2k views

Relation between chemical kinetics and chemical equilibrium

In my chemistry book, the law of chemical equilibrium is derived from the law of mass action: For a reversible chemical reaction $$\ce{aA +bB\rightleftharpoons cC + dD}$$ where $a$, $b$, $c$ and $d$...
9
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1answer
2k views

Why does the Gibbs free energy only correspond to non-expansion work?

It has been defined as the energy available for work other than expansion work. Why can't it be used for expansion work
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2answers
33k views

Strength of intramolecular vs intermolecular hydrogen bonds

Why are intramolecular hydrogen bonds weaker than intermolecular hydrogen bonds?
10
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3answers
347 views

Non-radiative transitions or what features of rhodamine result in it being so highly fluorescent?

Rhodamine is a fluorescent dye. What features of the molecule result in it being so highly fluorescent ? I assume the extended conjugated system with a stabilized first excited state is necessary, ...
10
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2answers
10k views

Why is CO practically nonpolar?

This question was in my book. According to me CO should be polar as it should have a dipole moment. But I found that the $\sigma$-electron drift from C to O is almost nullified by the $\pi$-electron ...
9
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2answers
861 views

Comparing formula for enthalpy change with bond dissociation energy and formation enthalpy

I learnt that given a reaction: $$\ce{A -> B}$$ the enthalpy change is given by: $$\Delta H = \left( \begin{array}{c} \text{total enthalpy of}\\ \text{bonds broken}\end{array}\right)-\left( \begin{...
25
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2answers
15k views

What is known about liquid carbon?

The wiki tells me that if you heat carbon at atmospheric pressure it eventually turns directly into a gas without being liquid first. At what pressure can you make liquid carbon? Has anyone actually ...