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Your presence information is a quick way for other people to see your availability status. Presence is automatically set based on your Outlook calendar, but you can change it manually if you want to.
As an example, if you have a meeting currently scheduled in Outlook, your status appears as 'In a meeting' in Skype for Business. When you're in a Skype for Business audio or video call, your presence indicator appears red, as Busy, and your status is updated to 'In a call.'
You can also manually set your presence status to include details you want others to see. your presence can also include a personal note that appears in your Contacts list and on your contact card. This gives people more information about what you're up to.

Mac Extraordinaire: If you just want to setup the default user that is logged in when you open Skype, you can do so by choosing to LOG OUT in Skype and log in with the Account that you wish to be setup as default.
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I've got a user who is trying to make calls using skype for business on a MacBook but when they do, the mic doesn't seem to be working. All of the audio settings are turned up full on the skype settings and the strange things is that in the system preferences I can see that the mic is picking up sound and working fine.

Change your presence status

Certain features and behaviors that are available to Skype for Business on Mac clients are determined by preference settings on the client. The Skype for Business on Mac preferences are found in a file located on Macs that have installed the Skype for Business client located at the following path.

Click the status menu drop-down arrow below your name on the Skype for Business main window, and then click the status you want to show other people.

To revert from the status you set and have Skype for Business automatically update your status, click the status menu and then click Reset Status.

Choose the appropriate status

Make sure you set your status accurately. The following table describes each presence status that other people may see for you, what each status means, and which ones you can set yourself.

Note: The presence statuses are pre-set in Skype for Business, which means you can't create a custom status, but you can give your contacts more details about where you are or what you're doing by adding a personal note.

If your presence is	It means you are	How this status gets set
Available	Online and available to contact.	Set automatically for you based on your keyboard activity or Outlook calendar. You can also set this status when you want others to know you’re in your office even though the computer is idle.
Be Right Back	Stepping away from the computer for a few moments.	You can set your presence to this anytime you want.
Away/Appear Away	Logged on but your computer has been idle, or you’ve been away from your computer for a specified (set by you) period of time.	Set automatically for you based on your keyboard activity or Outlook calendar. Skype for Business sets your status to “inactive” when your computer’s been idle for five minutes, and to “away” when your status has been inactive for five minutes. (To change these default values, click the Options button, click Status, and then click the arrows next to Show me as Inactive when my status has been idle for this many minutes and Show me as Away when my status has been Inactive for this many minutes.) You can also set your presence to this anytime you want.
Off Work	Not working and not available to be contacted.	You can set your presence to this anytime you want.
Busy	Busy and don’t want to be interrupted.	Set automatically for you based on your Outlook calendar. You can also set your presence to this anytime you want. If you manually set it to Busy, it will revert back to your Outlook calendar status in 24 hours, if you do not change it before then.
In a call	In a Skype for Business call (a two-way audio call) and don’t want to be disturbed.	Set automatically for you based on your phone activity.
In a meeting	In a meeting and don’t want to be disturbed.	Set automatically for you based on your Outlook calendar.
In a conference call	In a Skype for Business conference call (a Skype for Business meeting with audio) and don’t want to be disturbed.	Set automatically for you when you have joined a conference call or a meet now session.
Do Not Disturb	Don’t want to be disturbed and will see conversation notifications only if sent by someone in your workgroup.	You can set your presence to this anytime you want. If you manually set it to Do Not Disturb, it will revert back to your Outlook Calendar status in 24 hours, if you do not change your status before then.
Presenting	Giving a presentation and can’t be disturbed.	Set automatically for you when you are presenting in a Skype for Business meeting. You can change this setting in the Status options window.
Out of Office	You are out of the office.	Set automatically for you based on your Outlook calendar.
Out of the office(automatic reply is on)	You have set the automatic reply feature in Outlook.	Set automatically for you when you set automatic replies in Outlook.
Offline	Not signed in. You’ll appear as Offline to people whom you’ve blocked from seeing your presence.	Set automatically for you based on your keyboard activity or Outlook calendar.
Unknown	Your presence can't be detected.	This status might appear to contacts who are not using Skype for Business as their instant messaging program.

Note: If you use Outlook and your turn of the out-of-office notification, the note you write in Outlook displays in Skype for Business as well, and a red star or asterisk (*) appears next to your presence status at bottom of your picture display area.

Set Skype For Business As Default Mac