ap® chemistry: exploring atomic structure using photoelectron spectroscopy (pes) data with jamie...
TRANSCRIPT
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AP® Chemistry: Exploring Atomic Structure Using Photoelectron Spectroscopy (PES) Data
with Jamie Benigna
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Navigating the webcast
College Board Equity and Access Policies
Before we begin, a few words about …
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Navigating the Webcast
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Document Resources
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The College Board strongly encourages educators to make equitable access a guiding principle for their AP programs by giving all willing and academically prepared students the opportunity to participate in AP.
We encourage the elimination of barriers that restrict access to AP for students from ethnic, racial and socioeconomic groups that have been traditionally underserved.
Schools should make every effort to ensure their AP classes reflect the diversity of their student population.
The College Board also believes that all students should have access to academically challenging course work before they enroll in AP classes, which can prepare them for AP success.
It is only through a commitment to equitable preparation and access that true equity and excellence can be achieved.
Equity and Access Statement
4
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What does it mean to “provide all students with access to academically challenging course work before they enroll in AP classes?”
In what way has your math, science or STEM program already either addressed or been challenged by this goal?
What opportunities must be provided in the curricula at all grades to ideally prepare students to compete and succeed in a global economy?
Equity and Access: Guiding Questions
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Warm welcome to our instructor – Jamie Benigna!
Be sure to budget about 60 minutes to listen, read and complete the webcast and exercises
Time to begin …
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Jamie Benigna
• AP Chemistry Teacher, Department CoordinatorThe Roeper School, Birmingham, Michigan
• AP Exam Reader
• College Board Consultant
• Development Committee Member
• Food Stylist and Recipe Contributor to VizChef cooking app
Hello from the Instructor
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Chemists rely heavily on various methods of spectroscopy to understand the structure of atoms and molecules that are too small to see directly
Photoelectron Spectroscopy (PES) is a powerful instrumental tool for probing the electronic structure of any of the naturally-occurring elements, as well as materials that contain mixtures of these elements
This topic has been included in the redesigned AP® Chemistry course, and may not be well understood by students
Why a webcast on PES?
Image Source: SPECS GmbH
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Review the data that have led to various revisions of the atomic model
Investigate the basic setup of PES instrumentation
Explore the abilities and limitations of PES, and the analysis of the spectra produced by PES.
Share many examples of: • Spectra• Student handouts appropriate for classroom use• Sample assessment items
Reveal data sources and resources to learn more about PES
Course OverviewIn this webcast we will:
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How PES can be used to probe the electronic structure of atoms,
How the data from PES confirms the shell/subshell model of the atom,
How PES data can be used alongside instruction on electron configurations, electron shielding, and the quantum mechanical model
Learning Objectives By the end of this webcast, AP® Chemistry teachers will be prepared to teach:
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Setting the Stagewith a few foundational questions
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Setting the Stage
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PROPERTIES
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Introduction to Photoelectron Spectroscopy (PES)
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--- -
---
-- +
+
++ +
+
++
++++ +++
+- -
-
-
-
- --
Dalton Thomson Rutherford Bohr
++
+++++
+
Image sources:http://library.thinkquest.org/13394/angielsk/athompd.htmlhttp://abyss.uoregon.edu/~js/21st_century_science/lectures/lec11.html http://mail.colonial.net/~hkaiter/astronomyimages1011/hydrogen_emis_spect.jpghttp://upload.wikimedia.org/wikipedia/commons/9/97/A_New_System_of_Chemical_Philosophy_fp.jpg
Various Models of the Atom
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1s
2s
3s
4s
5s
6s
7s
2p
3p
4p
5p
6p
3d
4d
5d4f
5f
1s2s 2p3s 3p 3d4s 4p 4d 4f5s 5p 5d 5f6s 6p 6d7s 7p 8s
Further refinements to these models have occurred with new experimental results
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3d
4d
5d
6d
4f
5f
1s1s
4s
5s
6s
7s
3s
2s
4p
5p
6p
7p
3p
2pChromium
52.00
24
Cr
63.55
CuCopper
29
[Ar]4s13d5 [Ar]4s13d10
But not all elements ‘follow the rules’
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How do we know?
hν+
-
-
hν
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Image source: Dayah, Michael. “Dynamic Periodic Table.” Accessed Sept. 5, 2013. http://ptable.com/#Property/Ionization
Image source: http://chemistry.beloit.edu/stars/images/IEexpand.gif
Ionization Energy
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Element IE1 IE2 IE3 IE4 IE5 IE6 IE7
Na 495 4,560
Mg 735 1,445 7,730
Al 580 1,815 2,740 11,600
Si 780 1,575 3,220 4,350 16,100
P 1,060 1,890 2,905 4,950 6,270 21,200
S 1,005 2,260 3,375 4,565 6,950 8,490 27,000
Cl 1,255 2,295 3,850 5,160 6,560 9,360 11,000
Ar 1,527 2,665 3,945 5,770 7,230 8,780 12,000
LO 1.5 - The student is able to explain the distribution of electrons in an atom or ion based upon data.
LO 1.6 - The student is able to analyze data relating to electron energies for patterns or relationships.
Ionization Energy
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𝑬=𝒉𝝂
11+
--
-
-
- -
-
-
--
-hν
Radiation Type ν E Aspects Probed
Microwaves 109 – 1011 Hz 10-7 – 10-4 MJ/mol Molecular rotations
Infrared (IR) 1011 – 1014 Hz 10-4 – 10-1 MJ/mol Molecular vibrations
Visible (ROYGBV) 4x1014 – 7.5x1014 Hz 0.2 - 0.3 MJ/mol Valence electron transitions in atoms and molecules
Ultraviolet (UV) 1014 – 1016 Hz 0.3 – 100 MJ/mol Valence electron transitions in atoms and molecules
X-ray 1016 – 1019 Hz 102 – 105 MJ/mol Core electron transitions in atoms
hν
IE1 = 495 kJ/molIE1 = 0.495 MJ/mol
How do we probe further into the atom?
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𝝂=𝑬𝒉
=𝟏 .𝟎𝟑𝟑 ∙𝟏𝟎𝟖 𝑱 /𝒎𝒐𝒍𝟔 .𝟔𝟐𝟔 ∙𝟏𝟎−𝟑𝟒 𝑱 ∙ 𝒔
11+
--
-
-
- -
-
-
--
-hν
𝝂=𝟏 .𝟓𝟓𝟗 ∙𝟏𝟎𝟒𝟏𝒎𝒐𝒍−𝟏 ∙ 𝒔−𝟏
Radiation Type ν E Aspects Probed
X-ray 1016 – 1019 Hz 102 – 105 MJ/mol Core electron transitions in atoms
Removing Core Electrons
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11+
--
-
-
- -
-
-
--
-hν
hν 𝑬𝟏𝒔𝒕=𝟏𝟎𝟑 .𝟑𝑴𝑱 /𝒎𝒐𝒍𝑬𝟐𝒏𝒅=𝟑−𝟔𝑴𝑱 /𝒎𝒐𝒍
Any frequency of light that is sufficient to remove electrons from the 1st shell can remove electrons from any of the other shells.
Removing Core Electrons
= IE + KE
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PES Instrument
Image Source: SPECS GmbH, http://www.specs.de/cms/front_content.php?idart=267
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3+ 3+ 3+
3+ 3+ 3+
3+ 3+ 3+
3+ 3+
3+ 3+
3+ 3+ 3+
3+ 3+ 3+3+ 3+ 3+3+ 3+
3+ 3+ 3+3+3+ 3+
3+ 3+ 3+3+3+ 3+
3+ 3+ 3+3+ 3+ 3+3+3+
3+3+ 3+
3+3+3+3+3+3+
X-ray or UV Source
Kinetic Energy AnalyzerKinetic Energy Analyzer
Binding Energy (MJ/mol)6.26 0.52
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Kinetic Energy Analyzer
Negative Voltage Hemisphere
Slightly Less Negative Voltage
Hemisphere
1Volt=1 Joule1 Coulomb
1 e−=1.602 x10− 19Coulombs1 eV=1.602 x10−19 Joules
1mole of eV=96 485 J10.364 eV=1MJ /mol
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Negative Voltage Hemisphere
Positive Voltage Hemisphere
If Kinetic energy is too high…
Negative Voltage Hemisphere
Slightly Less Negative Voltage
Hemisphere
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Negative Voltage Hemisphere
Positive Voltage Hemisphere
If voltage is too high…
Negative Voltage Hemisphere
Slightly Less Negative Voltage
Hemisphere
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3+ 3+ 3+
3+ 3+ 3+
3+ 3+ 3+
3+ 3+
3+ 3+
3+ 3+ 3+
3+ 5+ 3+5+ 3+ 3+5+ 5+
3+ 5+ 3+5+5+ 5+
3+ 5+ 3+5+5+ 5+
3+ 3+ 3+3+ 5+ 3+5+5+
3+5+ 5+
3+3+5+3+3+5+
X-ray or UV Source
Kinetic Energy Analyzer
Binding Energy (MJ/mol)
Binding Energy (MJ/mol)19.3 0.80 1.36
Boron
6.26 0.52
Li
Kinetic Energy Analyzer
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Analyzing Data from PES Experiments
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Binding Energy (MJ/mol)
90 80 70 60 50 40 30 20 10 0
84.0 4.7
2.0
1s
2s
2p
+
Which of the following elements might this spectrum represent?
(A)He(B)N(C)Ne(D)Ar
Rela
tive
Num
ber o
f Ele
ctro
ns
Analyzing data from PES
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Binding Energy (MJ/mol)
100 10 1
151 1.09
1s2
2p6
Rela
tive
Num
ber o
f Ele
ctro
ns
12.1
7.9
0.58
Given the spectrum above, identify the element and its electron configuration:
2s2
3s2
3p1
(A)B (B)Al (C)Si (D)Na
Analyzing data from PES
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Real Spectrum
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11+
--
-
-
- -
-
-
- -
-hν
hν
Auger Transitions
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4
3.5
3
2.5
2
1.5
1
.5
0
Inte
nsity
(x10
5 cou
nts/
s)Real Spectrum
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6
5
4
3
2
1
0
Inte
nsity
(x10
3 cou
nts/
s)Copper vs. Chromium
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Inte
nsity
(x10
5 cou
nts/
s)
Binding Energy (MJ/mol)
4
3.5
3
2.5
2
1.5
1
0.5
100 90 80 70 60 50 40 30 20 10 0
Mixtures of Elements
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PES Sample Questions
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Sample Question #1Which element could be represented by the complete PES spectrum below?
(A) Li (B) B (C) N (D) Ne
0.1110100
Binding Energy (MJ/mol)
Re
lati
ve
Nu
mb
er
of
Ele
c-
tro
ns
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Sample Question #2
Which of the following best explains the relative positioning and intensity of the 2s peaks in the following spectra?
(A) Be has a greater nuclear charge than Li and more electrons in the 2s orbital(B) Be electrons experience greater electron-electron repulsions than Li electrons(C) Li has a greater pull from the nucleus on the 2s electrons, so they are harder to remove(D) Li has greater electron shielding by the 1s orbital, so the 2s electrons are easier to remove
Binding Energy (MJ/mol)14 12 10 8 6 4 2 0
Inte
nsi
ty
Be
Binding Energy (MJ/mol)14 12 10 8 6 4 2 0
Li
Inte
nsi
ty
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MJ/mol
Sulfur S
1.00
16.5
2.05 22.7 239
Sample Question #3Given the photoelectron spectra above for phosphorus, P, and sulfur, S, which of the following best explains why the 2p peak for S is further to the left than the 2p peak for P, but the 3p peak for S is further to the right than the 3p peak for P?
(A) S has a greater effective nuclear charge than P, and the 3p sublevel in S has greater electron repulsions than in P.(B) S has a greater effective nuclear charge than P, and the 3p sublevel is more heavily shielded in S than in P.(C) S has a greater number of electrons than P, so the third energy level is further from the nucleus in S than in P.(D) S has a greater number of electrons than P, so the Coulombic attraction between the electron cloud and the nucleus is greater in S than in P.
MJ/mol
Phosphorus P
1.06
13.5
1.95 18.7 208
Binding Energy
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Sample Question #4Looking at the complete spectra for Na and K below, which of the following would best explain the relative positioning of the 3s electrons?
Binding Energy (MJ/mol)
Inte
nsity
(c/s
)
130 105 90 75 60 45 30 15 0
Binding Energy (MJ/mol)
Inte
nsity
(c/s
)
400 350 300 250 200 150 100 50 0
Na
K
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Sample Question #4aLooking at the spectra for Na and K below, which of the following would best explain the difference in binding energy for the 3s electrons?
Binding Energy (MJ/mol)
Inte
nsity
(c/s
)
4 3.5 3 2.5 2 1.5 1 0.5 0
Na-
3s
K-3s
(A) K has a greater nuclear charge than Na(B) K has more electron-electron repulsions than Na(C) Na has one valence electron in the 3s sublevel(D) Na has less electron shielding than K
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Sample Question #4bLooking at the spectra for Na and K below, which of the following would best explain the difference in signal intensity for the 3s electrons?
(A) K has a greater nuclear charge than Na(B) K has more electron-electron repulsions than Na(C) Na has one valence electron in the 3s sublevel(D) Na has less electron shielding than K
Binding Energy (MJ/mol)
Inte
nsity
(c/s
)
4 3.5 3 2.5 2 1.5 1 0.5 0
Na-
3s
K-3s
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Sample Question #5Given the photoelectron spectrum below, which of the following best explains the relative positioning of the peaks on the horizontal axis?
(A) O has more valence electrons than Ti or C, so more energy is required to remove them
(B) O has more electron-electron repulsions in the 2p sublevel than Ti and C(C) Ti atoms are present in a greater quantity than O can C in the mixture.(D) Ti has a greater nuclear charge, but the 2p sublevel experiences greater
shielding than the 1s sublevel.
Inte
nsity
(cou
nts/
s)
Image source: http://www.rsc.org/ej/JM/2010/b925409a/b925409a-f2.gif
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Sample Question #6Given the photoelectron spectrum of scandium below, which of the following best explains why Scandium commonly makes a 3+ ion as opposed to a 2+ ion?
(A) Removing 3 electrons releases more energy than removing 2 electrons.
(B) Scandium is in Group 3, and atoms only lose the number of electrons that will result in a noble gas electron configuration
(C) The amount of energy required to remove an electron from the 3d sublevel is close to that for the 4s sublevel, but significantly more energy is needed to remove electrons from the 3p sublevel.
(D) Removing 2 electrons alleviates the spin-pairing repulsions in the 4s sublevel, so it is not as energetically favorable as emptying the 4s sublevel completely.
Binding Energy (MJ/mol)
Inte
nsity
(c/s
)
500 400 300 50 40 30 10 9 8 7 6 5 4 3 2 1 0
0.770.63
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Binding Energy (MJ/mol)100 10 1
Inte
nsity
Hint: for additional formative assessments, use spectra from previous multiple choice questions
Example Formative AssessmentOn the photoelectron spectrum of magnesium below, draw the spectrum for aluminum
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Quick Check – Can You Now Translate Between These Representations of Mg?
1s
2s
3s
4s
2p
3p
1s2 2s2 2p6 3s2
Binding Energy (MJ/mol)100 10 1
Inte
nsi
ty
Mg 12+
--
-
-
- -
-
-
- -
-
-
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image source: http://ericsaltchemistry.blogspot.com/2010/10/jj-thomsons-experiments-with-cathode.html
http://84d1f3.medialib.glogster.com/media/f9/f9a5f2402eb205269b648b14072d9fb3a2f556367849d7feb5cfa4a8e2b3fd29/yooouu.gif
--- -
---
-
- +
+
++ +
+
++
Thomson
++++ +++
+- -
-
-
-
--
-
Rutherford
++
+++++
+
Bohr
Using Data to Makes Conclusions About Atomic Structure
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Element IE1 IE2 IE3 IE4 IE5 IE6 IE7
Na 495 4560
Mg 735 1445 7730
Al 580 1815 2740 11,600
Si 780 1575 3220 4350 16,100
P 1060 1890 2905 4950 6270 21,200
S 1005 2260 3375 4565 6950 8490 27,000
Cl 1255 2295 3850 5160 6560 9360 11,000
Ar 1527 2665 3945 5770 7230 8780 12,000
Binding Energy (MJ/mol)100 10 1
151 1.09
1s2
2p6Re
lativ
e N
umbe
r of E
lect
rons
12.1
7.9
0.58
2s2 3s2 3p1
PES – Data that Shells are Divided into Subshells
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SP 3.2• The student can refine scientific questions
SP 3.3• The student can evaluate scientific questions
SP 6.3• The student can articulate the reasons that scientific
explanations are refined or replaced.
Applicable Science PracticesFrom the AP Chemistry Curriculum Framework:
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Wrap up and Take Aways
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1.5 – The student is able to explain the distribution of electrons in an atom or ion based upon data.
1.6 – The student is able to analyze data relating to electron energies for patterns and relationships.
1.7 – The student is able to describe the electronic structure of the atom, using PES data, ionization energy data, and/or Coulomb’s law to construct explanations of how the energies of electrons within shells in atoms vary.
1.8 – The student is able to explain the distribution of electrons using Coulomb’s law to analyze measured energies.
1.12 – The student is able to explain why a given set of data suggests, or does not suggest, the need to refine the atomic model from a classical shell model with the quantum mechanical model.
1.13 – Given information about a particular model of the atom, the student is able to determine if the model is consistent with specified evidence.
1.14 – The student can justify the selection of a particular type of spectroscopy to measure properties associated with vibrational or electronic motions of molecules.
Applicable Learning ObjectivesFrom the AP Chemistry Curriculum Framework:
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Classroom activities• Shells Class Activity• From Shells to Subshells Class Activity
Teacher resources• Spectrum generator spreadsheet• Peaks compiled (80 elements)• Frequently asked questions
Testing items• Sample items referenced in this webcast (for classroom
use, formative, or summative assessments)
Supporting ResourcesDownload and use the webcast handouts
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Arizona simulated photoelectron spectrahttp://www.chem.arizona.edu/chemt/Flash/photoelectron.html
Guided inquiry activities on PES• John Gelder (Oklahoma State University) • Moog and Farrell, Chemistry: A Guided Inquiry• POGIL
Books on PES technical specs• Van der Heide, Paul. X-Ray Photoelectron Spectroscopy: An
Introduction to Principles and Practices. New Jersey: John Wiley & Sons, Inc, 2012.
• Ellis, Andrew M., Miklos Feher, and Timothy Wright. Electronic and Photoelectron Spectroscopy: Fundamentals and Case Studies. New York: Cambridge University Press, 2005.
Supporting Resources (cont.)
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AP Chemistry Teacher Community (resources section)https://apcommunity.collegeboard.org/web/apchem
Spectra search strings• XPS• X-ray photoelectron spectroscopy• UVPS• ESCA spectroscopy• ESCA spectra• Photoelectron spectrum• Photoelectron spectroscopy
Supporting Resources (cont.)
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Supporting Resources (cont.)
Image Source: Shen Laboratory, Stanford University and SLAC National Accelerator Laboratoryhttp://arpes.stanford.edu/facilities_ssrl.html
Image source: Inna M Vishikhttp://www.stanford.edu/~ivishik/inna_vishik_files/Page452.htm
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Explaining how data informs our understanding of the atom
Using PES and experimental evidence to build mental models of atomic structure
Explaining how a PES instrument collects data and how to analyze spectra
Take Away
You should now feel confident
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Jamie Benigna AP Chemistry Development Committee [email protected]
Serena MagroganDirector, Science Curriculum and Content Development (AP Chemistry)[email protected]
Contact Information
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Complete a survey on the course and receive Jamie’s summer reading list!
Survey: https://www.surveymonkey.com/s/3FNCLPG
Thank you!